Sprayable, Aqueous Alcoholic Microbicidal Compositions Comprising Zinc Ions

ABSTRACT

Disclosed are pressurized surface treatment compositions which impart a microbicidal benefit to treated surfaces which compositions comprise (or in certain preferred embodiments may consist essentially of, or may consist of): a zinc ion source material which releases zinc ions into the treatment composition, preferably a source of Zn++ ions, at least lower alkyl aliphatic monohydric alcohol which independently of other constituents present exhibits a microbicidal effect, a propellant; and, water. The compositions may further optionally include one or more further optional constituents such as a detersive surfactant and/or minor amounts of one or more constituents which impart one or more advantageous technical or aesthetic benefits to the compositions, including one or more detersive surfactants wherein the compositions have pH of at least 5. The compositions exhibit a microbicidal or germicidal or antimicrobial effect on treated inanimate surfaces and are characterized in exhibiting a microbicidal benefit when tested against one or more challenge microorganisms, preferably against poliovirus type 1 (Sabin) [“PV1”], according to one or more of the following standardized test protocols: ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agents against Viruses in Suspension, or ASTM E1053 Standard Test Method to Assess Virucidal Activity of Chemicals Intended for Disinfection of Inanimate, Nonporous Environmental Surfaces, or European Standard Surface Test, EN13697, or AOAC Germicidal Spray Products as Disinfectant Test Method, AOAC Index, 17th Ed. (2000).

The present invention relates to sprayable, pressurized aqueousalcoholic compositions which comprise zinc ions which compositionsexhibit a microbicidal benefit when applied to inanimate surfaces. Thesesprayable pressurized aqueous alcoholic compositions provide asurprisingly high degree of microbicidal activity against variousundesirable microorganisms (sometimes referred to as ‘pathogens’)including various bacteria, mycobacteria, viruses, and fungi.

While ethanol and other monohydric alcohols are known to the art ashaving a beneficial microbicidal benefit, at the same time it is avolatile organic compound (“VOC”) and there is a substantial interest inregulating the use of ethanol (as well as other volatile organiccompounds) in products wherein the ethanol or other VOC is exposed tothe environment. Such regulatory interests are, however, completelycontrary to the technical benefits provided by ethanol and othermonohydric alcohols. Ethanol in particular is a very effectivemicrobicidal agent, as increased levels of ethanol in a composition havelong been known to exhibit increased microbicidal benefits againstundesirable microorganisms.

The technical art has proposed several compositions which are lauded toprovide some degree of antimicrobial efficacy, at the same timecomprising reduced amounts of ethanol and other monohydric alcoholswhile still providing an appreciable microbicidal benefit. However,these compositions are not wholly successful in providing a microbicidalbenefit against a broad range of undesirable microorganisms, and inparticular in providing effective microbicidal benefit againstparticularly difficult to eradicate microorganisms including viruses,and in particular poliovirus (e.g., poliovirus type 1 (Sabin)). As isrecognized in the art, demonstrated eradication of poliovirus is highlyadvantageous as such compositions would not only be effective incontrolling this dangerous microorganism but at the same time such ahigh level of efficacy would also be recognized as having a high degreeof microbicidal efficacy against relatively easier to eradicatemicroorganisms including but not limited to bacteria, mycobacteria,other non-enveloped and enveloped virus strains and in many cases,fungi.

The prior art discloses various compositions which are cited to providea microbicidal effect. For example, in U.S. Pat. No. 5,180,749 aredescribed largely aqueous compositions comprising about 65-88% wt. waterand which include as further essential constituents both about 10-30%wt. ethanol with about 2-5% wt. benzyl alcohol. However, the use ofwater soluble metal salts is not disclosed nor is the pH of thecompositions disclosed. The compositions were tested againstStaphylococcus aureus, Salmonella choleraesuis, Pseudomonas aeruginosa,rhinovirus type 39, herpes simplex 1, herpes simplex 2, adenovirus type2, respiratory syncytial, influenza A2, influenza B, human rotavirus,Mycobacterium tuberculosis var. bovis, as well as fungi of typesAspergillus niger and Trichopython mentgrophytes. In that patent, whencontrasting the data from Table B to the data from Table A, thenecessary inclusion of benzyl alcohol in conjunction with ethanol inorder to achieve increased microbicidal efficacy is shown. The poormicrobicidal efficacy of compositions comprising 30% wt. ethanol andwater and where benzyl alcohol is absent is demonstrated on Table B.

U.S. Pat. No. 5,728,404 discloses certain virucidal disinfectantcompositions which are described as including one or more C₁-C₄aliphatic alcohols, 0.1-1% wt. of a hydrolized metal ion, and water.Compositions comprising ethyl alcohol and isopropyl alcohol at ratios of8:1 to 1:1 are noted to be particularly effective and preferred. Whilethe document alleges that the amount of the aliphatic alcohol may be inthe range of 40%-90% wt., such is not demonstrated as in the only fourexamples provided the amount of the aliphatic alcohols are respectively80% wt., 70% wt., 80% wt. and 80% wt. Furthermore, when formed asdescribed in that patent document, the composition according to Example1 exhibited a pH of 5.48, the composition of Example 2 exhibited a pH of5.63, and the composition of Example 3 exhibited a pH of 5.63, whichindicates that the foregoing compositions consistently demonstrated anacidic pH.

The treatment of biofilms by compositions which include certain heavymetals are known from US 2008/0118573. The treatment steps require thatthe biofilms be contacted with the said compositions for 4 hours ormore. The biofilms are defined to be conglomerates of microbialorganisms embedded in highly hydrated matricies of exopolymers,typically polysaccharides, and other macromolecules.

U.S. Pat. Nos. 6,034,043 and 6,017,861 disclose liquid skin cleaningcompositions comprising (1) a so-called mild surfactant system, of whichat least 10% wt. of which, preferably at least 25% wt. of which, is ananionic surfactant, (2) 0.1-10% wt. of a polyvalent cation or cationsselected from zinc, copper, tin, aluminum, cobalt, nickel, chromium,titanium, and/or manganese and mixtures thereof, and (3) 1-99% wt. waterwherein the cations provide antimicrobial activity. The patent suggeststhat antimicrobial activity of the liquid skin cleaning compositions wasdue to the combination of the mild surfactant system with the polyvalentcation or cations which in combination, provided an antimicrobialbenefit whereas the polyvalent cation or cations themselves did not.None of the demonstrated compositions include lower alkyl monohydricalcohols.

U.S. Pat. No. 6,344,218 discloses topical sanitizing gel compositionswhich include an odor absorber, which may be a water soluble salt suchas a water soluble copper salt or water soluble zinc salt, from 40-90%wt. of an alcohol as well as an antimicrobial agent which may be aquaternary ammonium chloride. The reference states that when zinc saltsare used, the pH is suitable adjusted to less than about 7, preferablyless than about 6 and more preferably to less than about 5.

U.S. Pat. No. 7,871,649 discloses antimicrobially active gels, creams,ointments, lotions and soaps whose antimicrobial activity is enhanced bythe inclusion of quaternary ammonium compounds and essential oils and/orone or more individual constituents thereof. These compositions are fortopical application to the skin or various mucous membranes of the body.In preferred embodiments the compositions comprise 10-90% w/w alcohol,15-70% w/w water, 0.05-3% w/w thickeners and/or gelling agents, and0.1-3% w/w of emollients. The reference discloses that zinc salts may bepresent to reduce skin irritation of the gels. No mention of anyantimicrobial efficacy against poliovirus is disclosed.

US 2004/0213750 discloses aqueous alcoholic compositions which comprise40% wt.-70% wt. of a lower alkanol, optionally a quaternary ammoniumcationic compound which itself provides germicidal properties, water anda pH adjusting agent to provide a final pH of between 7 and 13. Thecompositions are shown to be effective against various microorganismsincluding gram-positive and gram-negative types of pathogenic bacteria,as well as poliovirus type 1 at a 10 minute contact time. The referencemakes no mention of the use of zinc ions in the compositions.

Further known to the art are the compositions disclosed in US2007/0184013 which compositions are cited to be effective againstnon-enveloped virus particles. The compositions comprise a C₁-C₆ alcoholand an efficacy-enhancing amount of one or more of: cationic oligomersand polymers, proton donors, chaotropic agents, and mixtures thereofwith the proviso that when the compositions include a proton donor, acationic oligomer or polymer is also present. The cationic oligomers andpolymers disclosed are defined to include cationic polyalkylene imines,cationic ethoxy polyalkylene imines, cationicpoly[N-[3-(dialkylammonio)alkyl]N′[3-(alkyleneoxyalkylenedialkylammonio)alkyl]urea dichloride], vinylcaprolactam/VP/dialkylaminoalkyl alkylate copolymers and polyquaterniumcopolymers. The example compositions disclosed in the referencedemonstrate compositions having 62% and even greater amounts of theC₁-C₆ alcohol as being present.

US 2008/0045491 discloses certain surface sanitizer compositions whichare recited to include 50-90% of an alcohol component, 10-50% of water,an acid component to maintain the pH of the composition between 2-5, and0.05-5% of a multivalent cation constituent. The multivalent cationconstituent may be a one of a selected list of polymers, a metal ion, ora metal compound. The compositions may optionally include one or morefurther constituents, including oxidative agents, plant derived alkenesor essential oils, emollients, humectants, lubricants and one or moreantimicrobial compounds, e.g., quaternary ammonium compounds. A singleexample of US 2008/0045491 demonstrates that a composition having 78%wt. ethanol exhibits efficacy against Candida albicans, Aspergillusniger, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureusand Adenovirus type 5. The further examples of US 2008/0045491 are notdisclosed to have been tested against any microorganisms.

US 2008/0138438 discloses certain antimicrobial compositions havingantiviral and antibacterial efficacy which include a divalent zinc salt,optionally a disinfecting alcohol, optionally an antimicrobial agent,and optionally an organic acid. The compositions exhibit a pH of about 5or less, preferably a pH of less than 4.5 and especially preferably a pHin the range of about 2.5 to about 4.5.

US 2010/0151046 discloses certain disinfectant compositions whichcomprise ethanol, a zinc containing compound which releases zinc ions insolution, and a combination of lactic acid with citric acid.

US 2010/0233098 discloses methods and compositions for disinfecting hardsurfaces which are aqueous compositions which comprise 40% wt.-70% wt.of an alcohol constituent selected from the group consisting ofmethanol, ethanol, n-propanol, isopropanol, n-butanol, benzyl alcohol,and mixtures thereof and a pH in the range of from about 7.0-14.0. Thecompositions may include further optional constituents, includingancillary antimicrobial agents, and surfactants. The use of watersoluble metal salts is not disclosed.

Notwithstanding these various known art compositions, there is still anurgent need in the art to produce pressurized, sprayable treatmentcompositions, particularly those adapted for the control or eradicationof undesired microorganisms where such treatment compositions comprisereduced amounts of VOC, and in particular aliphatic alcohols whichprovide a microbicidal effect such as ethanol, yet which compositionsare highly effective against particularly difficult to eradicateundesired microorganisms, especially poliovirus, particularly where thesprayable, pressurized treatment compositions are applied to aninanimate surface.

In a broad aspect, the compositions of the present invention aredirected to sprayable, pressurized inanimate surface treatmentcompositions which impart a microbicidal benefit to treated surfaceswhich compositions comprise (or in certain preferred embodiments mayconsist essentially of, or may consist of) as constituents: a zinc ionsource material which releases zinc ions into the treatment composition,at least one alcohol which independently of other constituents presentexhibits a microbicidal effect, and a liquid carrier which may be wateror a mixture of water and an alcohol, and a propellant, and wherein thecompositions are at a pH such that the sprayable, pressurized inanimatesurface treatment compositions exhibit a microbicidal effect on treatedsurfaces. The sprayable, pressurized inanimate surface treatmentcompositions may further optionally comprise one or more additionalconstituents which impart one or more advantageous technical oraesthetic benefits to the compositions, e.g., one or more cationicquaternary ammonium compounds which provide a microbicidal benefit, oneor more detersive surfactants. Preferably the sprayable, pressurizedinanimate surface treatment compositions are characterized in exhibitinga microbicidal benefit when tested according to one or more of thefollowing standardized test protocols: ASTM E1052 Standard Test Methodfor Efficacy of Antimicrobial Agents against Viruses in Suspension, orASTM E1053 Standard Test Method to Assess Virucidal Activity ofChemicals Intended for Disinfection of Inanimate, NonporousEnvironmental Surfaces, or European Standard Surface Test, EN13697, orAOAC Germicidal Spray Products as Disinfectant Test Method, AOAC Index,17^(th) Ed. (2000) against one or more challenge microorganisms.

Within this broad aspect, the present inventors have surprisinglyobserved that there may be formed sprayable pressurized treatmentcompositions which exhibit a synergistic improvement in microbiocidaleffect when there are added to aqueous alcoholic liquid compositions atspecific pH ranges, especially preferably at alkaline pH ranges, smallbut effective amounts of a material which provides a zinc ion to thesecompositions and optionally but in most cases, especially wherein atleast one further surfactant is also present. Such an effect issurprising, and also particularly technically advantageous, as improvedmicrobiocidal efficacy has been observed against particularly difficultto control (or eradicate) microorganisms and in particular thepoliovirus, while at the same time achieving these effects in aqueousalcoholic liquid compositions having a reduced VOC content. As is knownto the art, non-enveloped viruses including poliovirus is particularlydifficult to control or eradicate, and demonstrated microbiocidalefficacy against poliovirus is expected to be indicative of microbicidalefficacy against other non-enveloped viruses and microorganisms whichare less difficult to control or eradicate.

In one aspect the present invention provides sprayable, pressurizedinanimate surface treatment compositions which impart a microbicidalbenefit to treated surfaces which compositions comprise (or in certainpreferred embodiments may consist essentially of, or may consist of) asconstituents:

a zinc ion source material which releases zinc ions into the treatmentcomposition, preferably a source of Zn⁺⁺ ions;

at least one lower alkyl aliphatic monohydric alcohol;

propellant;

water;

optionally, one or more further constituents which impart one or moreadvantageous technical or aesthetic benefits to the compositions,including one or more detersive surfactants;

wherein the composition has a pH of at least 5,

wherein the compositions are characterized in exhibiting a microbicidalbenefit when tested against one or more challenge microorganisms,especially preferably against Poliovirus type 1 (Sabin) (“PV1”)according to one or more of the following standardized test protocols:ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agentsagainst Viruses in Suspension, or ASTM E1053 Standard Test Method toAssess Virucidal Activity of Chemicals Intended for Disinfection ofInanimate, Nonporous Environmental Surfaces, or European StandardSurface Test, EN1369, or AOAC Germicidal Spray Products as DisinfectantTest Method, AOAC Index, 17^(th) Ed. (2000).

In a second aspect the present invention provides sprayable, pressurizedinanimate surface treatment compositions which impart a microbicidalbenefit to such treated surfaces which compositions comprise (or incertain preferred embodiments may consist essentially of, or may consistof) as constituents:

a zinc ion source material which releases zinc ions into the treatmentcomposition, preferably a source of Zn⁺⁺ ions;

in excess of 0% wt., and up to but excluding 20% wt. of at least onelower alkyl aliphatic monohydric alcohol;

propellant;

optionally but preferably also at least one quaternary ammoniumsurfactant compound which provides a microbicidal benefit;

water;

optionally, one or more further constituents which impart one or moreadvantageous technical or aesthetic benefits to the compositions,including one or more detersive surfactants;

wherein the composition has a pH of at least 5,

wherein the compositions are characterized in exhibiting a microbicidalbenefit when tested against one or more challenge microorganisms,especially preferably against poliovirus type 1 (Sabin) (“PV1”)according to one or more of the following standardized test protocols:ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agentsagainst Viruses in Suspension, or ASTM E1053 Standard Test Method toAssess Virucidal Activity of Chemicals Intended for Disinfection ofInanimate, Nonporous Environmental Surfaces, or European StandardSurface Test, EN13697, or AOAC Germicidal Spray Products as DisinfectantTest Method, AOAC Index, 17^(th) Ed. (2000) against one or morechallenge microorganisms, especially preferably against poliovirus type1 (Sabin) (“PV1”).

In a third aspect the present invention provides sprayable, pressurizedinanimate inanimate surface treatment compositions which impart amicrobicidal benefit to such treated surfaces which compositionscomprise (or in certain preferred embodiments may consist essentiallyoff, or may consist of) as constituents:

a zinc ion source material which releases zinc ions into the treatmentcomposition, preferably a source of Zn⁺⁺ ions;

at least one lower alkyl aliphatic monohydric alcohol;

at least one further detersive surfactant, other than the least onequaternary ammonium compound, which provides a microbicidal benefit, ascompared to where such at least one such further detersive surfactant isabsent, which is preferably at least one nonionic surfactant;

propellant;

water;

optionally, one or more further constituents which impart one or moreadvantageous technical or aesthetic benefits to the compositions,including one or more detersive surfactants;

wherein the composition has a pH of at least 5,

wherein the compositions are characterized in exhibiting a microbicidalbenefit against one or more challenge microorganisms, especiallypreferably against poliovirus type 1 (Sabin) (“PV1”), when testedaccording to one or more of the following standardized test protocols:ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agentsagainst Viruses in Suspension, or ASTM E1053 Standard Test Method toAssess Virucidal Activity of Chemicals Intended for Disinfection ofInanimate, Nonporous Environmental Surfaces, or European StandardSurface Test, EN13697, or AOAC Germicidal Spray Products as DisinfectantTest Method, AOAC Index, 17^(th) Ed. (2000).

In a fourth aspect the present invention provides sprayable, pressurizedinanimate surface treatment compositions which impart a microbicidalbenefit to treated surfaces which compositions comprise (or in certainpreferred embodiments may consist essentially of, or may consist of) asconstituents:

a zinc ion source material which releases zinc ions into the treatmentcomposition, preferably a source of Zn⁺⁺ ions;

at least 20% wt of at least one lower alkyl aliphatic monohydricalcohol;

at least one quaternary ammonium surfactant compound which provides amicrobicidal benefit;

at least one further detersive surfactant, other than the least onequaternary ammonium compound, which provides a microbicidal benefit, ascompared to where such at least one such further detersive surfactant isabsent, which is preferably at least one nonionic surfactant;

propellant,

water;

optionally, one or more further constituents which impart one or moreadvantageous technical or aesthetic benefits to the compositions,including one or more detersive surfactants;

wherein the composition has a pH of at least 5,

wherein the surface treatment compositions are characterized inexhibiting a microbicidal benefit against one or more challengemicroorganisms, especially preferably against poliovirus type 1 (Sabin)(“PV1”), when tested according to one or more of the followingstandardized test protocols: ASTM E1052 Standard Test Method forEfficacy of Antimicrobial Agents against Viruses in Suspension, or ASTME1053 Standard Test Method to Assess Virucidal Activity of ChemicalsIntended for Disinfection of Inanimate, Nonporous EnvironmentalSurfaces, or European Standard Surface Test, EN13697, or AOAC GermicidalSpray Products as Disinfectant Test Method, AOAC Index, 17^(th) Ed.(2000).

In a fifth aspect the present invention provides liquid, inanimatesurface treatment compositions which impart a microbicidal benefit tosuch treated surfaces which compositions comprise (or in certainpreferred embodiments may consist essentially of, or may consist of) asconstituents:

a zinc source material which releases zinc ions into the treatmentcomposition, preferably a source of Zn++ ions;

at least 35% wt. of at least one lower alkyl aliphatic monohydricalcohol, and wherein

-   -   a) when compositions comprise 35% wt. to <39% wt. of at least        one lower alkyl aliphatic monohydric alcohol, the pH of the        compositions are ≥10 and <11;    -   b) when compositions comprise ≥39% wt. to ≤50% wt. of at least        one lower alkyl aliphatic monohydric alcohol, the pH of the        compositions are ≥9 and <11;

at least one quaternary ammonium compound which provides a microbicidalbenefit;

water;

propellant;

optionally, one or more further constituents which impart one or moreadvantageous technical or aesthetic benefits to the compositions,including one or more detersive surfactants;

and,

wherein the surface treatment compositions are characterized inexhibiting at least a 3 log 10 result when tested against poliovirustype 1 (Sabin) (“PV1”) tested according to one or more of the followingstandardized test protocols: ASTM E1052 Standard Test Method forEfficacy of Antimicrobial Agents against Viruses in Suspension, or, ASTME1053 Standard Test Method to Assess Virucidal Activity of ChemicalsIntended for Disinfection of Inanimate, Nonporous EnvironmentalSurfaces.

In the foregoing, preferably at least one detersive surfactant is alsopresent, preferably a nonionic surfactant, as a further essentialconstituent.

In a further aspect the present invention provides sprayable,pressurized treatment compositions according to any foregoing aspects ofthe invention which compositions exhibit a pH of at least at least 6,yet more preferably at least 7.

In a further aspect the present invention provides a sprayable,pressurized treatment composition according to any of the foregoingaspects of the invention, which compositions are further characterizedin the composition satisfies at least one of the following Conditions A,B, C, D, E, F, G, H, I, J, K and L:

log₁₀ reduction of % wt. of at poliovirus type 1 least one (Sabin)(“PV1”)when lower alkyl tested according to aliphatic the standardizedtest Con- pH or pH monohydric protocol: ASTM dition range alcohol E1052A   <9 ≥38.6 and ≤45 — B ≥9.0 and <9.5 ≥34.15 and ≤45.44 at least 1.73 C≥9.5 and <10 ≥37.4 and ≤45.44 at least 5.0 D ≥10 and <10.5 ≥35.2 and≤45.44 at least 5.0 E ≥10.5 and ≥31.8 and ≤45.44 at least 7.0 <11 F ≥11≥31.8 and ≤45.44 — log₁₀ reduction of % wt. of at poliovirus type 1least one (Sabin) (“PV1”)when lower alkyl tested according to aliphaticthe standardized test Con- pH or pH monohydric protocol: ASTM ditionrange alcohol E1053 G   <9 ≥38.6 and ≤40.9 — H ≥9.0 and <9.5 ≥34.15 and≤45.44 — I ≥9.5 and <10 ≥37.4 and ≤45.44 at least 3.73 J ≥10 and <10.5≥35.2 and ≤45.44 at least 2.25 K ≥10.5 and ≥31.8 and ≤45.44 at least3.17 <11 L ≥11 ≥31.8 and ≤45.44 at least 4.17

In a further aspect the present invention provides a sprayable,pressurized treatment composition according to any of the foregoingaspects of the invention, which compositions are further characterizedin the composition satisfies at least one of the following Conditions M,N, O, P, Q, R, S and T.

log₁₀ reduction of % wt. of at poliovirus type 1 least one (Sabin)(“PV1”) when lower alkyl tested according to aliphatic the standardizedtest Con- monohydric pH or pH protocol: ASTM dition alcohol range E1052M  <37.1 ≥9.11 and ≤11.51 at least 1.73 N ≥37.1 and <40 ≥9.17 and ≤10.44at least 3.27 O ≥40 and <43 ≥8.49 and ≤11.5 at least 7.0 P ≥43 ≥8.74 and≤11.03 at least 2.56 log₁₀ reduction of % wt. of at poliovirus type 1least one (Sabin) (“PV1”) when lower alkyl tested according to aliphaticthe standardized test Con- monohydric pH or pH protocol: ASTM ditionalcohol range E1053 Q  <37.1 ≥9.11 and ≤11.51 — R ≥37.1 and <40 ≥9.17and ≤10.44 at least 0.38 S ≥40 and <43 ≥8.49 and ≤11.5 at least 3.05 T≥43 ≥9.0 and ≤11.03 at least 2.0

In a still further aspect the present invention provides a method ofcontrolling the incidence of undesired microorganisms on an inanimatesurface, the method comprising the step of contacting an inanimatesurface which is in need of treatment or upon which the presence of oneor more undesirable microorganisms are suspected or are known to bepresent, with an effective amount of a sprayable, pressurized inanimatesurface treatment composition as described herein to provide a surfacetreatment benefit thereto, to provide a microbicidal benefit to thecontacted surface.

In an additional aspect the present invention provides a vendibleproduct, as well as a method for the manufacture of such a vendibleproduct which comprises a sprayable, pressurized inanimate surfacetreatment composition as described herein.

These and further aspects of the invention will become more apparentfrom a reading of the following specification.

A first essential constituent of the invention is a zinc ion sourcematerial which provides zinc ions which are compounds, constituents ormaterials which are at least partially soluble in the aqueous alcoholicbase of the inventive compositions Preferably such compounds,constituents or materials release zinc ions (e.g., preferably Zn++)within the inventive compositions. Nonlimiting examples of such includezinc compounds having a counterion selected from acetate,acetylacetonate, bromide, bromide, citrate, chloride, formate,gluconate, glycerophosphate, iodide, lactate, nitrate, salycilate,sulfate, pyrithione and tartrate. By way of non-limiting example, suchinclude species such as zinc acetate, zinc butyrate, zinc citrate, zincchloride, zinc gluconate, zinc glycolate, zinc glycerate, zincglycolate, zinc formate, zinc lactate, zinc monohydrate, zincpicolinate, zinc proprionate, zinc salycilate, zinc sulfate, zinctartrate, and zinc undecylenate. The zinc ion source may be in ahydrated form. The zinc ion source may comprise one or more saidcompounds, constituents or materials. Preferred zinc ion sources includezinc salts of an organo-carboxylic acid having from about 2 to about 6carbon atoms, such as zinc salts of acetates, glycloates, lactates,gluconate and citrates. Particularly preferred zinc ion sources aredisclosed in one or more of the Examples.

The zinc ion source materials need not be fully soluble within thetreatment compositions provided by the present invention and may, forexample, be dispersions.

The zinc ion source material may be present in the treatmentcompositions in any effective amount and may provide as little as about0.5 ppm (part per million) of the zinc ion to the composition, butadvantageously is present in an amount of at least about 0.001% wt. toabout 2.5% wt, preferably from about 0.01% wt to about 1% wt., andparticularly preferably from about 0.01% wt. to about 0.5% wt.Alternately, the zinc ion source material may be present in thetreatment compositions in a sufficient amount such that the zinc ionsource material releases zinc ions, and preferably Zn++ ions, into thetreatment composition so to provide between about 1 ppm to about 10,000ppm of zinc ions, preferably to about (in order of increasingpreference) 9500, 9000, 8500, 8000, 7500, 7000, 6750, 6500, 6250, 6000,5750, 5500, 5250, 5000, 4750, 4500, 4250, 4000, 3750, 3500, 3250, 3000,2750, 2500, 2400, 2300, 2250, 2200, 2100, 2000, 1900, 1800, 1750, 1700,1650, 1600, 1550, 1500, 1450, 1400, 1350, 1300, 1250, 1200, 1150, 1100,1050, 1000, 975, 950, 925, 900, 875, 850, 825, 800, 775, 750, 725, 700,675, 650, 625, 600, 575, 550, 500, 475, 450, 425, 400, 375, 350, 325,300, 275, 250, 225, 200, 175, 150, 125, 100, 95, 90, 85, 80, 75, 70, 65,60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1ppm, and/or alternately any integer number value within the above rangeof 1-10,000 ppm of zinc ions, within the inventive compositions taughtherein.

Exclusive of counterions of surfactant compounds or counterions of othermaterials described herein which might be present, most preferably thezinc source material is the sole material present in the compositionwhich releases available metal ions to the treatment compositions taughtherein. Most preferably the zinc source material is the sole materialpresent in the composition which releases available metal ions to thetreatment compositions taught herein.

A further essential constituent of the inventive compositions is atleast one lower alkyl aliphatic monohydric alcohol. Preferably this atleast one lower alkyl aliphatic monohydric alcohol also exhibits abiocidal effect against microorganisms independently of the otherconstituents which may be present in the compositions. Exemplary andpreferred are C₁-C₆ mononhydric alcohols, especially methanol, ethanol,n-propanol, isopropanol, and all isomers of butanol. Of these, C₁-C₄monohydric alcohols, and especially C₁-C₃ mononhydric alcohols arepreferred, especially, ethanol. A single such alcohol, or mixture of twoor more such alcohols, may be present. In certain embodiments when aplurality of alcohols are present, ethanol is the predominant alcoholpresent, and especially preferably comprises at least 50.1% wt., andespecially preferably and in order of increasing preference, at least51%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 92%, 95%, 97%, 98%, 99%,99.5% and 100% by weight of the at least one lower alkyl aliphaticmonohydric alcohol constituent present. The at least one lower alkylaliphatic monohydric alcohol constituent may be present in any amount inexcess of 0% wt., but preferably is present in amount of at least about0.01% wt., and in order of increasing preference in amounts of at leastabout 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%,6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%,13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%,19%, 19.% by weight of the composition of which they form a part.Preferably the at least one lower alkyl aliphatic monohydric alcoholconstituent is present in the pressurized, sprayable treatmentcomposition in an amount of at least about 20% wt., and in order ofincreasing preference comprises at least 22%, 22.5%, 23%, 23.5%, 24%,24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5% 28%, 28.5%, 29%, 29.5%, 30%,30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%,36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40%, 40.5%, 41%, 41.5%, 42%,42.5%, 43%, 43.5%, 44%, 44.5%, 45%, 45.5%, 46%, 46.5%, 47%, 47.5%, 48%,48.5%, 49%, 49.5%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% and 70% by weight.Concurrently and preferably the at least one lower alkyl aliphaticmonohydric alcohol constituent is present in the pressurized, sprayabletreatment composition in an amount of up to about 70% by weight, and inorder of increasing preference comprises at least about 69%, 68%, 67%,66%, 65%, 64%, 63%, 62%, 61%, 60%, 59%, 58%, 57%, 56%, 55%, 54%, 53%,52%, 51%, 50%, 49.5%, 49%, 48.5%, 48%, 47.5%, 47%, 46.5%, 46%, 45.5%,45%, 44.5% 44%, 43.5%, 43%, 42.5%, 42%, 41.5%, 41%, 40.5%, 40%, 39.5%,39%, 38.5%, 385, 37.5%, 37%, 36.5%, 36%, 35.5%, 35%, 34.5%, 34%, 33.5%,33%, 32.5%, 32%, 31.5%, 31%, 30.5%, 30%, 29.5%, 29%, 28.5%, 28%, 27.5%,27%, 26.5%, 26%, 25.5%, 25%, 24.5%, 24%, 23.5%, 23%, 22.5%, 22%, 21.5%,21%, 20% by weight of the pressurized, sprayable treatment compositionof which it forms a part, although lesser amounts of at least about19.5%, 19%, 18.5%, 18%, 17.5%, 17%, 16.5%, 16%, 15.5%, 15%, 14.5%, 14%,13.5%, 13%, 12.5%, 12%, 11.5%, 11%, 10.5%, 10%, 9.5%, 9%, 8.5%, 8%,7.5%, 7%, 6.5%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%,0.5%, and even as little a about 0.1% wt. or about 0.01% wt.

In certain preferred embodiments the compositions preferably comprisefrom 20% wt. to 40% wt. of at least one lower alkyl aliphatic monohydricalcohol, and preferably in an amount up to but excluding 40% wt., andespecially preferably where ethanol was the predominant or sole alkylaliphatic monohydric alcohol present in the lower alkyl aliphaticmonohydric alcohol constituent.

In certain preferred embodiments the compositions preferably comprisefrom about 40% wt. to about 50% wt., of at least one lower alkylaliphatic monohydric alcohol, and especially preferably where ethanolwas the predominant or sole alkyl aliphatic monohydric alcohol presentin the lower alkyl aliphatic monohydric alcohol constituent.

In certain preferred embodiments the compositions preferably comprisefrom about 0.01% wt. to up to, but excluding 20% wt., of at least onelower alkyl aliphatic monohydric alcohol, and especially preferablywhere ethanol was the predominant or sole alkyl aliphatic monohydricalcohol present in the lower alkyl aliphatic monohydric alcoholconstituent.

Advantageously the lower alkyl aliphatic monohydric alcohol constituentexhibits a microbicidal effect against one or more pathogens even in theabsence of the further constituents of the pressurized, sprayabletreatment compositions taught herein. For this reason, C₁-C₃ monohydricaliphatic alcohols, e.g., methanol, ethanol and the various isomers ofpropanol are particularly preferred whether used singly or in mixturesof two or more selected C₁-C₃ monohydric aliphatic alcohols as the soleconstituents of the lower alkyl aliphatic monohydric alcoholconstituent. In certain embodiments a single C₁-C₃ monohydric aliphaticalcohol is present as the second essential constituent. In certainfurther preferred embodiments, ethanol is the sole constituent of thelower alkyl aliphatic monohydric alcohol constituent.

A next essential constituent is a propellant constituent. The propellantmay be a material or composition which is conventionally used in the artfor such purposes. Propellants which may be used include, for example, ahydrocarbon, of from 1 to 10 carbon atoms, such as n-propane, n-butane,isobutane, n-pentane, isopentane, and mixtures thereof; dimethyl etherand blends thereof as well as individual or mixtures of chloro-,chlorofluoro- and/or fluorohydrocarbons- and/or hydrochlorofluorocarbons(HCFCs). Useful commercially available compositions include A-70(aerosol compositions with a vapor pressure of 70 prig available fromcompanies such as Diversified and Aeropress) and Dymel® 152a(1,1-difluoroethane from DuPont). Compressed gases such as carbondioxide, compressed air, nitrogen, and possibly dense or supercriticalfluids may also be used, and in view of environmental benefits may bepreferred for use in many applications wherein the use of hydrocarbonbased, and particularly wherein the use of chloro-, chlorofluoro- and/orfluorohydrocarbons- and/or hydrochlorofluorocarbons (HCFCs) aredesirably avoided. Individual materials or blends of materials may beused as the propellant constituent. Advantageously the propellant willgenerally be present in an amount of from about 1% to about 50% of thetotal formulation as contained within the aerosol canister, withpreferred amounts being from about 1% to about 25%, more preferably fromabout 1% to about 15%.

Alternately the propellant constituent may provide an additional 1% wt.to about 20% wt., preferably about an additional 1% wt. to about 12% wt.in addition to the balance of the remaining constituents present in thesprayable, pressurized, liquid, inanimate surface treatment compositionswhich had been or are formulated to provide a “100% wt.” composition, towhich the propellant constituent is subsequently added. Such a manner ofcalculating the weight percentages of the non-propellant constituents ina sprayable, pressurized, liquid, inanimate surface treatmentcomposition is convenient as it is expected and understood that afterbeing dispensed from an aerosol canister, the propellant is rapidlyflashed off into the atmosphere and is not believed to nor has beenobserved to provide any microbicidal benefit or to enhance anymicrobicidal benefit or effect of the remaining constituents present ina composition.

Water is a fourth essential constituent of the invention. The water maybe tap water, but is preferably distilled and is most preferablydeionized water. If the water is tap water, it is preferablysubstantially free of any undesirable impurities such as organics orinorganics, especially mineral salts which are present in hard water andwhich may undesirably interfere with the operation of the constituentspresent in the compositions according to the invention. Preferably watercomprises at least about 10% wt. and more preferably in order ofincreasing preference at least about 105, 11%, 12%, 13%, 14%, 15%, 16%,17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%,31%, 32%, 33%. 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%,45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%,59%, 60%, 61%, 62%, 63%, 64%, 65%. 66%, 67%, 68%, 69%, 70%, 71%, 72%,73%, 74%, and 75% by weight of water. Concurrently, the compositions ofthe invention preferably comprise not more than about 75% wt., water,and in order of increasing preference comprise not more than about: 74%,73%, 72%, 71%, 70%, 695, 68%, 67%, 66%, 65%. 64%, 63%, 62%, 61%, 60%,59%, 58%, 57%, 56%. 55%, 54%. 53%, 52%, 51%. 50%, 49%, 48%, 47%. 46%,45%, 44%, 43%, 42%, 41%, 40%, 39%, 38%. 37%, 36%, 35%, 34%, 33%, 32%,31%, 30%, 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%. 21% 20%, 19%, 185,17%, 16%, 15%, 14%, 13%, 12%, 11%, 10% by weight of water. In preferredembodiments the total amount of water and the at least one lower alkylaliphatic monohydric alcohol(s) present comprise at least 80% wt., yetmore preferably and in order of increasing preference comprise at least81%. 82%, 83%. 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%. 92%, 93%, 94%,95%, 96%, 97%, 98%, and 99% by weight of the compositions of which theyform a part.

The present inventors have found that these four essential constituents,when at a pH of 5 or greater, preferably 6 or greater, form a highlyeffective system which exhibits a high degree of microbicidal efficacyeven in the absence of further constituents. Advantageously however thissystem may be supplemented by one or more further constituents.

While not wishing to be bound by the following, the present inventorshave surprisingly found that by careful selection of: (1) the nature andamounts of the zinc ion source material which releases zinc ions intothe treatment composition, and especially preferably wherein the zincion source material is a source of Zn⁺⁺ ions, (2) the at least onealiphatic monohydric alcohol which itself exhibits an independentmicrobicidal effect, (3) water, (4) propellant, and (5) the pH level ofthe sprayable, pressurized surface treatment composition, the resultantcompositions provide unexpectedly excellent microbicidal efficacyagainst a range of undesirable microorganisms including certain viruses,bacteria and certain fungi, which has heretofore not been expected fromcompositions which include the reduced amounts of the alcoholconstituent provided in the inventive compositions. The resultantcompositions provide unexpectedly excellent microbicidal efficacyagainst a range of undesirable microorganisms including certain viruses,bacteria and certain fungi, which has heretofore not been expected fromcompositions which include the reduced amounts of the alcoholconstituent provided in the inventive compositions. Such an effect hasbeen observed even when a very limited amount of the zinc ion sourcematerial is present, and wherein the amount of the one lower alkylaliphatic monohydric alcohol is also present in reduced amounts, e.g, inamount of to about 50% wt., or even lesser amounts. Reference is made tothe various Examples provided in this patent specification whichdemonstrates this effect, particularly as against comparativeformulations which omit one or more of the essential constituents.Although the literature describes the biochemical mechanisms of theseparate microbicidal actives when these microbicidal actives are usedsingly, surface treatment compositions as now disclosed by the inventorsare believed to be unknown, particularly wherein such surface treatmentcompositions exhibit what is believed to be a synergistic benefit.

In a further aspect of the invention there is provided a microbicidalcontrol system of constituents which are in and of themselves effectivein providing effective control of poliovirus independently of furtherand optional constituents. This microbicidal control system ofconstituents comprises (or consists essentially of, or consists of):water, propellant, one or more one or more C₁-C₄ aliphatic alcoholswhich independently of other constituents present exhibits amicrobicidal effect, and especially preferably wherein ethanol is thepredominant or sole C₁-C₄ aliphatic alcohols present, a zinc ion sourcematerial which is preferably a source of Zn⁺⁺ ions, optionally at leastone cationic quaternary ammonium compound which provides a microbicidalbenefit, optionally at least one further detersive surfactant other thanthe said cationic quaternary ammonium compound, which optional furtherdetersive surfactant provides an improvement to the treatmentcomposition in the control of poliovirus, as compared to where such atleast one such further detersive surfactant is absent, which at leastone further detersive surfactant is preferably at least one nonionicsurfactant and further, and where necessary, a buffer or pH adjustingagent to impart an alkaline pH, preferably an alkaline pH of 7.5 orgreater. In preferred embodiments, the microbial control system furtherincludes the least one further detersive surfactant, other than aquaternary ammonium surfactant compound which provides a microbicidalbenefit, which further detersive surfactant is preferably at least onenonionic surfactant. Preferably the microbicidal control system ischaracterized in exhibiting a microbicidal benefit when tested,especially preferably against poliovirus type 1 (Sabin) (“PV1”), againstone or more challenge microorganisms according to one or more of thefollowing standardized test protocols: ASTM E1052 Standard Test Methodfor Efficacy of Antimicrobial Agents against Viruses in Suspension, orASTM E1053 Standard Test Method to Assess Virucidal Activity ofChemicals Intended for Disinfection of Inanimate, NonporousEnvironmental Surfaces, or European Standard Surface Test, EN1369, orAOAC Germicidal Spray Products as Disinfectant Test Method, AOAC Index,17^(th) Ed. (2000).

In certain preferred embodiments the microbicidal control system ofconstituents necessarily includes one or both of the at least onecationic quaternary ammonium compound which provides a microbicidalbenefit, and/or at least one further detersive surfactant.

In a further aspect, an additional essential constituent of theforegoing antimicrobial control system is at least one further detersivesurfactant, other than a cationic quaternary ammonium compound whichprovides a microbicidal benefit, which further detersive surfactantprovides an improvement to the control of poliovirus b the treatmentcomposition, as compared to where such at least one such furtherdetersive surfactant is absent, which at least one further detersivesurfactant is preferably at least one nonionic surfactant.

In a further aspect of the invention there is provided a secondmicrobicidal control system of constituents which are in and ofthemselves effective in providing effective control of Polio virusindependently of further and optional constituents. This furthermicrobiocidal control system of constituents comprises (or consistsessentially of, or consists of): water, propellant, a zinc ion source,preferably which releases Zn⁺⁺ ions, one or more one or more C₁-C₄aliphatic alcohols which independently of other constituents presentexhibits a microbicidal effect and especially preferably wherein ethanolis the predominant or sole C₁-C₄ aliphatic alcohols present, at leastone quaternary ammonium compound which provides a microbicidal benefit,and where necessary a buffer or pH adjusting agent to impart an alkalinepH, and preferably an alkaline pH of 7.5 or greater. Optionally butpreferably the surfactant constituent is one or both of a nonionicsurfactant and/or a cationic surfactant which itself provides a furthermicrobiocidal benefit. This second microbicidal control system ofconstituents may thereafter optionally include further constituentswhich may or may not provide a further microbiocidal benefit. Preferablythis second microbicidal control system of constituents includes as afurther essential at least one further detersive surfactant, other thana cationic quaternary ammonium compound which provides a microbicidalbenefit, which further detersive surfactant provides an improvement tothe control of poliovirus by the treatment composition, as compared towhere such at least one such further detersive surfactant is absent,which at least one further detersive surfactant is preferably at leastone nonionic surfactant.

Preferably this second microbicidal control system is characterized inexhibiting a microbicidal benefit, especially preferably againstpoliovirus type 1 (Sabin) (“PV1”), when tested against one or morechallenge microorganisms according to one or more of the followingstandardized test protocols: ASTM E1052 Standard Test Method forEfficacy of Antimicrobial Agents against Viruses in Suspension, or ASTME1053 Standard Test Method to Assess Virucidal Activity of ChemicalsIntended for Disinfection of Inanimate, Nonporous EnvironmentalSurfaces, or European Standard Surface Test, EN13697, or AOAC GermicidalSpray Products as Disinfectant Test Method, AOAC Index, 17^(th) Ed.(2000).

Any of the foregoing microbicidal control systems of constituents may beincluded in sprayable, pressurized treatment composition which includefurther additional constituents and thus form a part thereof.Alternately, any of the foregoing microbicidal control systems ofconstituents may of themselves be representative of an effectivesprayable, pressurized treatment composition. Thus, in thisspecification any disclosure or discussions relevant to or sprayable,pressurized liquid treatment compositions may be considered similarlyapplicable and relevant to the microbial control systems disclosedherein.

The sprayable, pressurized surface treatment compositions may furtheroptionally comprise one or more additional constituents which impart oneor more advantageous technical or aesthetic benefits to thecompositions.

Optionally but in many cases, the sprayable, pressurized treatmentcompositions preferably further comprise at least one quaternaryammonium compound which provides a microbicidal benefit (germicidalbenefit). Thus in certain embodiments one or more such quaternaryammonium compounds may be essential constituents. For the purposes ofthe present invention described herein, such quaternary ammoniumcompounds are to be understood as being outside of the scope of thedefined further detersive surfactants as such materials are primarilyprovided to impart a microbicidal effect, and not provide an appreciabledetersive benefit. Any cationic surfactant which satisfies theserequirements may be used and are is considered to be within the scope ofthe present invention. Mixtures of two or more cationic surface activeagents, viz., cationic surfactants may also be used. Cationicsurfactants are well known, and useful cationic surfactants may be oneor more of those described for example in McCutcheon's FunctionalMaterials, Vol. 2, 1998; Kirk-Othmer, Encyclopedia of ChemicalTechnology, 4th Ed., Vol. 23, pp. 481-541 (1997), the contents of whichare herein incorporated by reference. These are also described in therespective product specifications and literature available from thesuppliers of these cationic surfactants.

Examples of preferred cationic surfactant compositions useful in thepractice of the instant invention are those which provide an ancillarymicrobicidal or germicidal effect to the compositions, and especiallypreferred are quaternary ammonium compounds and salts thereof, which maybe characterized by the general structural formula:

where at least one of R₁, R₂, R₃ and R₄ is a alkyl, aryl or alkylarylsubstituent of from 6 to 26 carbon atoms, and the entire cation portionof the molecule has a molecular weight of at least 165. The alkylsubstituents may be long-chain alkyl, long-chain alkoxyaryl, long-chainalkylaryl, halogen-substituted long-chain alkylaryl, long-chainalkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on thenitrogen atoms other than the abovementioned alkyl substituents arehydrocarbons usually containing no more than 12 carbon atoms. Thesubstituents R₁, R₂, R₃ and R₄ may be straight-chained or may bebranched, but are preferably straight-chained, and may include one ormore amide, ether or ester linkages. The counterion X may be anysalt-forming anion which permits for the solubility of the quaternaryammonium complex within the treatment composition.

Exemplary quaternary ammonium salts within the above description includethe alkyl ammonium halides such as cetyl trimethyl ammonium bromide,alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammoniumbromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide,and the like. Other suitable types of quaternary ammonium salts includethose in which the molecule contains either amide, ether or esterlinkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammoniumchloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and thelike. Other very effective types of quaternary ammonium compounds whichare useful as germicides include those in which the hydrophobic radicalis characterized by a substituted aromatic nucleus as in the case oflauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethylammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate,dodecylbenzyltrimethyl ammonium chloride, chlorinateddodecylbenzyltrimethyl ammonium chloride, and the like.

Preferred quaternary ammonium compounds which act as germicides andwhich are useful in the practice of the present invention include thosewhich have the structural formula:

wherein R₂ and R₃ are the same or different C₈-C₁₂alkyl, or R₂ isC₁₂₋₁₆alkyl. C₈₋₁₈alkylethoxy, C₈₋₁₈alkylphenolethoxy and R₃ is benzyl,and X is a halide, for example chloride, bromide or iodide, asaccharinate counterion or is a methosulfate anion. The alkyl groupsrecited in R₂ and R₃ may be straight-chained or branched, but arepreferably substantially linear.

Particularly useful quaternary ammonium compounds include compositionswhich include a single quaternary compound, as well as mixtures of twoor more different quaternary compounds. Such useful quaternary compoundsare available under the BARDAC®, BARQUAT®, HYAMINE®, LONZABAC®, andONYXIDE® trademarks, which are more fully described in, for example,McCutcheon's Functional Materials (Vol. 2), North American Edition,1998, as well as the respective product literature from the suppliersidentified below. Such include, for example, BARDAC® 205M which isdescribed to be a liquid containing alkyl dimethyl benzyl ammoniumchloride, octyl decyl dimethyl ammonium chloride; didecyl dimethylammonium chloride, and dioctyl dimethyl ammonium chloride (50% active)(also available as 80% active (BARDAC® 208M)); BARDAC® 2050 which isdescribed to be a combination of octyl decyl dimethyl ammoniumchloride/didecyl dimethyl ammonium chloride, and dioctyl dimethylammonium chloride (50% active) (also available as 80% active (BARDAC®2080)); BARDAC® 2250 which is described to be didecyl dimethyl ammoniumchloride (50% active); BARDAC® LF (or BARDAC® LF-80), described as beingbased on dioctyl dimethyl ammonium chloride (BARQUAT® MB-50, MX-50,OJ-50 (each 50% liquid) and MB-80 or MX-80 (each 80% liquid) are eachdescribed as an alkyl dimethyl benzyl ammonium chloride; BARDAC® 4250and BARQUAT® 4250Z (each 50% active) or BARQUAT® 4280 and BARQUAT 4280Z(each 80% active) are each described as alkyl dimethyl benzyl ammoniumchloride/alkyl dimethyl ethyl benzyl ammonium chloride. Also, HYAMINE®1622, described as diisobutyl phenoxy ethoxy ethyl dimethyl benzylammonium chloride (50% solution); HYAMINE® 3500 (50% actives), describedas alkyl dimethyl benzyl ammonium chloride (also available as 80% active(HYAMINE® 3500-80)); and HYMAINE® 2389 described as being based onmethyldodecylbenzyl ammonium chloride and/ormethyldodecylxylene-bis-trimethyl ammonium chloride. (BARDAC®, BARQUAT®and HYAMINE® are presently commercially available from Lonza, Inc.,Fairlawn, N.J.). BTC® 50 NF (or BTC® 65 NE) is described to be alkyldimethyl benzyl ammonium chloride (50% active); BTC® 99 is described asdidecyl dimethyl ammonium chloride (50% active); BTC® 776 is describedto be myrisalkonium chloride (50% active); BTC® 818 is described asbeing octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammoniumchloride, and dioctyl dimethyl ammonium chloride (50% active) (availablealso as 80% active (BTC® 818-80%)); BTC® 824 and BTC® 835 are eachdescribed as being of alkyl dimethyl benzyl ammonium chloride (each 50%active); BTC® 885 is described as a combination of BTC® 835 and BTC® 818(50% active) (available also as 80% active (BTC® 888)); BTC© 1010 isdescribed as didecyl dimethyl ammonium chloride (50% active) (alsoavailable as 80% active (BTC® 1010-80)); BTC® 2125 (or BTC® 2125 M) isdescribed as alkyl dimethyl benzyl ammonium chloride and alkyl dimethylethylbenzyl ammonium chloride (each 50% active) (also available as 80%active (BTC® 2125 80 or BTC® 2125 M)); BTC® 2565 is described as alkyldimethyl benzyl ammonium chlorides (50% active) (also available as 80%active (BTC® 2568)); BTC® 8248 (or BTC® 8358) is described as alkyldimethyl benzyl ammonium chloride (80% active) (also available as 90%active (BTC® 8249)); ONYXIDE® 3300 is described as n-alkyl dimethylbenzyl ammonium saccharinate (95% active). (BTC® and ONYXIDE® arepresently commercially available from Stepan Company, Northfield, Ill.)Polymeric quaternary ammonium salts based on these monomeric structuresare also considered desirable for the present invention. One example isPOLYQUAT®, described as being a 2-butenyldimethyl ammonium chloridepolymer.

When present, the quaternary ammonium compound(s) may be present in anyeffective amount, but generally need not be present in amounts in excessof about 10% wt. based on the total weight of the composition of whichit forms a part. When present, preferably the microbicidal quaternaryammonium compounds may be present in the inventive compositions inamounts of from about 0.001% wt. to up to about 10% wt., very preferablyabout 0.01-8% wt., more preferably in amounts of between about 0.01-2%wt., and most preferably from about 0.01-1% wt. It is particularlyadvantageous that the preferred microbicidal cationic surfactant(s) arepresent in amounts of at least about 200 parts per million (ppm),preferably in amounts of from about 1 ppm to about 10,000 ppm,preferably from about 50 ppm to about 2000 ppm, more preferably inamounts of from about 100 ppm to about 1,000 ppm. Particularly preferredamounts of one or more quaternary ammonium compound(s) and preferredamounts are identified with reference to the examples.

In certain preferred embodiments the treatment compositions necessarilyinclude at least at least one further detersive surfactant, (which ispreferably a nonionic surfactant) other than a germicidally effectivequaternary ammonium compound, which least one further detersivesurfactant provides a further microbicidal benefit within the treatmentcomposition of which it forms a part, as compared to where such at leastone such further detersive surfactant is absent from said composition.

In certain embodiments the treatment compositions necessarily include atleast one further, detersive surfactant, although such may be consideredan optional constituent according to other embodiments of the invention.

In certain preferred embodiments the treatment compositions necessarilyinclude at least one further detersive surfactant, (which is preferablya nonionic surfactant) other than a germicidally effective quaternaryammonium compound, which at least one further detersive surfactantprovides a further microbicidal benefit within the treatment compositionof which it forms a part, as compared to where such at least one suchfurther detersive surfactant is absent from said composition.

In certain embodiments the treatment compositions necessarily include atleast one further, detersive surfactant, although such may be consideredan optional constituent according to other embodiments of the invention.

Non-limiting examples of the major surfactant types that can be used asdetersive surfactants of the present invention include those which areknown as anionic, nonionic, amphoteric, and zwitterionic surfactants aswell as further cationic surfactants which are not primarily present toprovide a microbicidal or germicidal benefit. Such include, e.g.:sulfates and sulfonates of oils and fatty acids, sulfates andsulfonates, ethoxylated alkylphenols, sulfates of alcohols, sulfates ofethoxylated alcohols, sulfates of fatty esters, sulfonates of benzene,cumene, toluene and xylene, sulfonates of condensed naphthalenes,sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthaleneand alkyl naphthalene, sulfonates of petroleum, sulfosuccinamates,sulfosuccinates and derivatives, soaps, taurates, thio and mercaptoderivatives, tridecyl and dodecyl benzene sulfonic acids, alkanolamides,alkanolamines, alkylaryl sulfonates, alkylaryl sulfonic acids,alkylbenzenes, amine acetates, amine oxides, amines, sulfonated aminesand amides, betaine derivatives, block polymers, carboxylated alcohol oralkylphenol ethoxylates, carboxylic acids and fatty acids, ethoxylatedalcohols, ethoxylated alkylphenols, ethoxlated amines and/or amides,ethoxylated fatty acids, ethoxylated fatty esters and oils, fattyesters, fluorocarbon-based surfactants, glycerol esters, glycol esters,hetocyclic-type products, imidazolines and imidazoline derivatives,isethionates, lanolin-based derivatives, lecithin and lecithinderivatives, lignin and lignin deriviatives, maleic or succinicanhydrides, methyl esters, monoglycerides and derivatives, olefinsulfonates, phosphate esters, phosphorous organic derivatives,polyethylene glycols, polymeric (polysaccharides, acrylic acid, andacrylamide) surfactants, propoxylated and ethoxylated fatty acidalcohols or alkyl phenols, protein-based surfactants, sarcosinederivatives, silicone-based surfactants, sorbitan derivatives, sucroseand glucose esters and derivatives, as well as further surfactants knownto the art but not elucidated here.

Typically however the use of anionic surfactants is to be avoided assuch would be expected to form insoluble complexes quaternary ammoniumcompound which provides a germicidal or microbicidal benefit isconcurrently present.

Additional non-limiting examples of surfactants that can be used tocarry out the present invention include one or more nonionicsurfactants, especially one or more compounds based on the condensationproducts of alkylene oxide groups with an organic hydrophobic compound,such as an aliphatic compound or with an alkyl aromatic compound. Thenonionic synthetic organic detergents generally are the condensationproducts of an organic aliphatic or alkyl aromatic hydrophobic compoundand hydrophilic ethylene oxide groups. Practically any hydrophobiccompound having a carboxy, hydroxy, amido, or amino group with a freehydrogen attached to the nitrogen can be condensed with ethylene oxideor with the polyhydration product thereof, polyethylene glycol, to forma water soluble nonionic detergent. Further, the length of thepolyethenoxy hydrophobic and hydrophilic elements may be varied toadjust these properties. Illustrative examples of such a nonionicsurfactant include the condensation product of one mole of an alkylphenol having an alkyl group containing from 6 to 12 carbon atoms withfrom about 5 to 25 moles of an alkylene oxide. Another example of such anonionic surfactant is the condensation product of one mole of analiphatic alcohol which may be a primary, secondary or tertiary alcoholhaving from 6 to 18 carbon atoms with from 1 to about 10 moles ofalkylene oxide. Preferred alkylene oxides are ethylene oxides orpropylene oxides which may be present singly, or may be both present.

Non-limiting, illustrative examples of nonionic surfactants includeprimary and secondary linear and branched alcohol ethoxylates, such asthose based on C₆-C₁₈ alcohols which further include an average of from2 to 80 moles of ethoxylation per mol of alcohol. Examples include theGenapol® series of linear alcohol ethoxylates from Clariant Corp.,Charlotte, N.C. The 26-L series is based on the formula RO(CH₂CH₂O)_(n)Hwherein R is a mixture of linear, even carbon-number hydrocarbon chainsranging from C₁₂H₂₅ to C₁₆H₃₃ and n represents the number of repeatingunits and is a number of from 1 to about 12, such as 26-L-1, 26-L-1.6,26-L-2, 26-L-3, 26-L-5, 26-L-45, 26-L-50, 26-L-60, 26-L-60N, 26-L-75,26-L-80, 26-L-98N, and the 24-L series, derived from synthetic sourcesand typically contain about 55% C₁₂ and 45% C₁₄ alcohols, such as24-L-3, 24-L-45, 24-L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and24-L-98N. From product literature, the single number following the “L”corresponds to the average degree of ethoxylation (numbers between 1 and5) and the two digit number following the letter “L” corresponds to thecloud point in ° C. of a 1.0 wt. % solution in water.

Further examples of useful nonionic surfactants include secondaryC₁₂-C₁₅ alcohol ethoxylates, including those which have from about 3 toabout 10 moles of ethoxylation. Such are available in the Tergitol®series of nonionic surfactants (Dow Chemical, Midland, Mich.),particularly those in the Tergitol® “15-S-” series. Further exemplarynonionic surfactants include linear primary C₁₁-C₁₅ alcohol ethoxylates,including those which have from about 3 to about 10 moles ofethoxylation. Such are available in the Tomadol® series of nonionicsurfactants under the following tradenames: Tomadol 1-3 (linear C₁₁alcohol with 3 moles (average) of ethylene oxide); Tomadol 1-5 (linearC₁₁ alcohol with 5 moles (average) of ethylene oxide); Tomadol 1-7(linear C₁₁ alcohol with 7 moles (average) of ethylene oxide); Tomadol1-9 (linear C₁₁ alcohol with 9 moles (average) of ethylene oxide);Tomadol 23-1 (linear C₁₂₋₁₃ alcohol with 1 mole (average) of ethyleneoxide); Tomadol 23-3 (linear C₁₂₋₁₃ alcohol with 3 moles (average) ofethylene oxide); Tomadol 23-5 (linear C₁₂₋₁₃ alcohol with 5 moles(average) of ethylene oxide); Tomadol 23-6.5 (linear C₁₂₋₁₃ alcohol with6.6 moles (average) of ethylene oxide); Tomadol 25-12 (linear C₁₂₋₁₅alcohol with 11.9 moles (average) of ethylene oxide); Tomadol 25-3(linear C₁₂₋₁₅ alcohol with 2.8 moles (average) of ethylene oxide);Tomadol 25-7 (linear C₁₂₋₁₅ alcohol with 7.3 moles (average) of ethyleneoxide); Tomadol 25-9 (linear C₁₂₋₁₅ alcohol with 8.9 moles (average) ofethylene oxide); Tomadol 45-13 (linear C₁₄₋₁₅ alcohol with 12.9 moles(average) of ethylene oxide); Tomadol 45-2.25 (linear C₁₄₋₁₅ alcoholwith 2.23 moles (average) of ethylene oxide); Tomadol 45-7 (linearC₁₄₋₁₅ alcohol with 7 moles (average) of ethylene oxide); Tomadol 91-2.5(linear C₉₋₁₁ alcohol with 2.7 moles (average) of ethylene oxide);Tomadol 91-6 (linear C₉₋₁₁ alcohol with 6 moles (average) of ethyleneoxide); Tomadol 91-8 (linear C₉₋₁₁ alcohol with 8.3 moles (average) ofethylene oxide) (Tomah Products, Inc., Milton, Wis.).

Further examples of useful nonionic surfactants include C₆-C₁₅ straightchain alcohols ethoxylated with about 1 to 13 moles of ethylene oxide,particularly those which include about 3 to about 6 moles of ethyleneoxide. Examples of such nonionic surfactants include Alfonic® 810-4.5,which is described as having an average molecular weight of 356, anethylene oxide content of about 4.85 moles and an HLB of about 12;Alfonic® 810-2, which is described as having an average molecular weightof 242, an ethylene oxide content of about 2.1 moles and an HLB of about12; and Alfonic® 610-3.5, which is described as having an averagemolecular weight of 276, an ethylene oxide content of about 3.1 moles,and an HLB of 10.

A further class of nonionic surfactants which may find use in thepresent inventive compositions include ethoxylated octyl and nonylphenols include those having one of the following general structuralformulas:

in which the C₉H₁₉ group in the latter formula is a mixture of branchedchained isomers, and x indicates an average number of ethoxy units inthe side chain. Particularly suitable non-ionic ethoxylated octyl andnonyl phenols include those having from about 7 to about 13 ethoxygroups. Such compounds are commercially available under the trade nameTriton® X (Dow Chemical, Midland, Mich.), as well as under the tradenameIgepal® (Rhodia, Princeton, N.J.). One exemplary and particularlypreferred nonylphenol ethoxylate is Igepal® CO-630.

Still further examples of suitable nonionic surfactants include whichmay be advantageously included in the inventive compositions are alkoxyblock copolymers, and in particular, compounds based on ethoxy/propoxyblock copolymers. Polymeric alkylene oxide block copolymers includenonionic surfactants in which the major portion of the molecule is madeup of block polymeric C2-C4 alkylene oxides. Such nonionic surfactants,while preferably built up from an alkylene oxide chain starting group,and can have as a starting nucleus almost any active hydrogen containinggroup including, without limitation, amides, phenols, thiols andsecondary alcohols.

One group of such useful nonionic surfactants containing thecharacteristic alkylene oxide blocks are those which may be generallyrepresented by the formula (A):

HO-(EO)_(x)(PO)_(y)(EO)_(z)-H  (A)

where EO represents ethylene oxide,

PO represents propylene oxide,

y equals at least 15,(EO)_(x+z) equals 20 to 50% of the total weight of said compounds, and,the total molecular weight is preferably in the range of about 2000 to15,000.

Another group of nonionic surfactants for use in the new inventivecompositions can be represented by the formula (B):

R-(EO,PO)_(a)(EO,PO)_(b)-H  (B)

wherein R is an alkyl, aryl or aralkyl group, where the R group contains1 to 20 carbon atoms, the weight percent of EO is within the range of 0to 45% in one of the blocks a, b, and within the range of 60 to 100% inthe other of the blocks a, b, and the total number of moles of combinedEO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in thePO rich block and 5 to 100 moles in the EO rich block.

Further nonionic surfactants which in general are encompassed by formula(B) include butoxy derivatives of propylene oxide/ethylene oxide blockpolymers having molecular weights within the range of about 2000-5000.

Still further useful nonionic surfactants containing polymeric butoxy(BO) groups can be represented by formula (C) as follows:

RO-(BO)_(n)(EO)_(x)-H  (C)

wherein R is an alkyl group containing 1 to 20 carbon atoms,

n is about 5-15 and x is about 5-15.

Also useful as the nonionic block copolymer surfactants, which alsoinclude polymeric butoxy groups, are those which may be represented bythe following formula (D):

HO-(EO)_(x)(BO)_(n)(EO)_(y)-H  (D)

wherein n is about 5-15, preferably about 15,

x is about 5-15, preferably about 15, and

y is about 5-15, preferably about 15.

Still further useful nonionic surfactants include ethoxylatedderivatives of propoxylated ethylene diamine, which may be representedby the following formula:

where (EO) represents ethoxy,

(PO) represents propoxy,

the amount of (PO)_(x) is such as to provide a molecular weight prior toethoxylation of about 300 to 7500, and the amount of (EO)_(y) is such asto provide about 20% to 90% of the total weight of said compound.

Further examples of useful nonionic surfactants are one or more amineoxides. Exemplary amine oxides include:

A) Alkyl di (lower alkyl) amine oxides in which the alkyl group hasabout 10-20, and preferably 12-16 carbon atoms, and can be straight orbranched chain, saturated or unsaturated. The lower alkyl groups includebetween 1 and 7 carbon atoms. Examples include lauryl dimethyl amineoxide, myristyl dimethyl amine oxide, and those in which the alkyl groupis a mixture of different amine oxide, dimethyl cocoamine oxide,dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityldimethyl amine oxide;

B) Alkyl di (hydroxy lower alkyl) amine oxides in which the alkyl grouphas about 10-20, and preferably 12-16 carbon atoms, and can be straightor branched chain, saturated or unsaturated. Examples arebis(2-hydroxyethyl) cocoamine oxide, bis(2-hydroxyethyl) tallowamineoxide; and bis(2-hydroxyethyl) stearylamine oxide;

C) Alkylamidopropyl di(lower alkyl) amine oxides in which the alkylgroup has about 10-20, and preferably 12-16 carbon atoms, and can bestraight or branched chain, saturated or unsaturated. Examples arecocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethylamine oxide; and

D) Alkylmorpholine oxides in which the alkyl group has about 10-20, andpreferably 12-16 carbon atoms, and can be straight or branched chain,saturated or unsaturated.

Preferably the amine oxide constituent is an alkyl di (lower alkyl)amine oxide as denoted above and which may be represented by thefollowing structure:

wherein each:

R₁ is a straight chained C₁-C₄ alkyl group, preferably both R₁ aremethyl groups; and,

R₂ is a straight chained C₈-C₁₈ alkyl group, preferably is C₁₀-C₁₄ alkylgroup, most preferably is a C₁₂ alkyl group.

Each of the alkyl groups may be linear or branched, but most preferablyare linear. Technical grade mixtures of two or more amine oxides may beused, wherein amine oxides of varying chains of the R₂ group arepresent. Preferably, the amine oxides used in the present inventioninclude R₂ groups which comprise at least 50% wt., preferably at least60% wt. of C₁₂ alkyl groups and at least 25% wt. of C₁₄ alkyl groups,with not more than 15% wt. of C₁₆, C₁₈ or higher alkyl groups as the R₂group.

Further specific examples of useful nonionic surfactants arealkanolamide surfactant compounds. Exemplary useful alkanolamidesinclude one or more monoethanol amides, and diethanol amides of fattyacids having an acyl moiety which contains from about 8 to about 18carbon atoms, and which may be represented in accordance with theformula:

R₁—CO—N(H)_(m-1)(R₂OH)_(3-m)

where R₁ represents a saturated or unsaturated aliphatic hydrocarbonradical of from about 7 to 21 carbon atoms, but preferably from about 11to 17 carbon atoms; R₂ represents a —CH₂— or —CH₂CH₂—, and m is aninteger from 1 to 3, but is preferably 1. Preferably, R₁ is a saturatedor unsaturated aliphatic hydrocarbon radical comprising from about 11 to17 carbon atoms, and m is 1. Specific examples of such compounds includemono-ethanol amine coconut fatty acid amide and diethanol amine dodecylfatty acid amide. An exemplary useful and particularly preferred fattyacid amides include cocomonoethanol amide or cocodiethanolamide, whichare presently commercially available under the Monamid® tradename.Further exemplary useful alkanolamides which provide such functionsinclude inter alia: cocamide MEA, cocamide DEA, soyamide DEA, lauramideDEA, oleamide MIPA, stearamide MEA, myristamide MEA, lauramide MEA,capramide DEA, ricinoleamide DEA, myristamide DEA, stearamide DEA,oleylamide DEA, tallowamide DEA, lauramide MIPA, tallowamide MEA,isostearamide DEA, isostearamide MEA, and mixtures thereof. Furtheruseful alkanolamide surfactant compounds include alkanolamides,particularly fatty monoalkanolamides and fatty dialkanolamides,including one or more of those marketed under the Ninol® tradename.Further exemplary alkanolamide surfactant compounds include monoethanolamides and diethanol amides include those marketed under the trade namesAlakamide® and Cyclomide® by Rhone-Poulenc Co., (Cranbury, N.J.) e.g.,Cyclomide® CDD-518 described to be a nonionic surfactant based oncoconut diethanolamide; Cyclomide® C212 described to be a nonionicsurfactant based on coconut monoethanolamide; Cyclomide® DC212/SEdescribed to be a nonionic surfactant based on 1:1 fatty aciddiethanolamide; Cyclomide® DIN 100 described to be a nonionic surfactantbased on lauric/linoleic diethanolamide; Cyclomide® DIN-295/S describedto be a nonionic surfactant based on 1:1 linoleic diethanolamide;Cyclomide® DL203 described to be a nonionic surfactant based on 2:1lauric diethanolamide.

Further specific examples of useful nonionic surfactants include alkylpolyglycosides. The alkyl polyglycosides which can be used as nonionicsurfactants in the composition are generally represented by the formula:

R₁O(R₂O)_(b)(Z)_(a)

wherein R₁ is a monovalent organic radical having from about 6 to about30 carbon atoms; R₂ is a divalent alkylene radical having from 2 to 4carbon atoms; Z is a saccharide residue having 5 or 6 carbon atoms; b isa number having a value from 0 to about 12; a is a number having a valuefrom 1 to about 6. Preferred alkyl polyglycosides have the formula Iwherein Z is a glucose residue and b is zero. Such alkyl polyglycosidesare commercially available, for example, as APG®, GLUCOPON®, orPLANTAREN® surfactants from Cogis Corp. Specific examples of suchsurfactants include but are not limited to: APG® 225, described to be analkyl polyglycoside in which the alkyl group contains 8 to 10 carbonatoms and having an average degree of polymerization of 1.7; GLUCOPON®425, described to be an alkyl polyglycoside in which the alkyl groupcontains 8 to 16 carbon atoms and having an average degree ofpolymerization of 1.48; GLUCOPON® 625, described to be an alkylpolyglycoside in which the alkyl group contains 12 to 16 carbon atomsand having an average degree of polymerization of 1.6; APG® 325,described to be an alkyl polyglycoside in which the alkyl group contains9 to 11 carbon atoms and having an average degree of polymerization of1.5; GLUCOPON® 600, described to be an alkyl polyglycoside in which thealkyl group contains 12 to 16 carbon atoms and having an average degreeof polymerization of 1.4; PLANTAREN® 2000, described to be an alkylpolyglycoside in which the alkyl group contains 8 to 16 carbon atoms andhaving an average degree of polymerization of 1.4; and, PLANTAREN® 1300,described to be an alkyl polyglycoside in which the alkyl group contains12 to 16 carbon atoms and having an average degree of polymerization of1.6. Other examples include alkyl polyglycoside surfactant compositionswhich are comprised of mixtures of compounds of formula I wherein Zrepresents a moiety derived from a reducing saccharide containing 5 or 6carbon atoms; a is a number having a value from 1 to about 6; b is zero;and R.sub.1 is an alkyl radical having from 8 to 20 carbon atoms. Thecompositions are characterized in that they have increased surfactantproperties and an HLB in the range of about 10 to about 16 and anon-Flory distribution of glycosides, which is comprised of a mixture ofan alkyl monoglycoside and a mixture of alkyl polyglycosides havingvarying degrees of polymerization of 2 and higher in progressivelydecreasing amounts, in which the amount by weight of polyglycosidehaving a degree of polymerization of 2, or mixtures thereof with thepolyglycoside having a degree of polymerization of 3, predominate inrelation to the amount of monoglycoside, said composition having anaverage degree of polymerization of about 1.8 to about 3. Suchcompositions, also known as peaked alkyl polyglycosides, can be preparedby separation of the monoglycoside from the original reaction mixture ofalkyl monoglycoside and alkyl polyglycosides after removal of thealcohol. This separation may be carried out by molecular distillationand normally results in the removal of about 70-95% by weight of thealkyl monoglycosides. After removal of the alkyl monoglycosides, therelative distribution of the various components, mono- andpoly-glycosides, in the resulting product changes and the concentrationin the product of the polyglycosides relative to the monoglycosideincreases as well as the concentration of individual polyglycosides tothe total. i.e. DP2 and DP3 fractions in relation to the sum of all DPfractions. Such compositions are disclosed in U.S. Pat. No. 5,266,690,the entire contents of which are incorporated herein by reference.

Other alkyl polyglycosides which can be used in the compositionsaccording to the invention are those in which the alkyl moiety containsfrom 6 to 18 carbon atoms in which and the average carbon chain lengthof the composition is from about 9 to about 14 comprising a mixture oftwo or more of at least binary components of alkylpolyglycosides,wherein each binary component is present in the mixture in relation toits average carbon chain length in an amount effective to provide thesurfactant composition with the average carbon chain length of about 9to about 14 and wherein at least one, or both binary components,comprise a Flory distribution of polyglycosides derived from anacid-catalyzed reaction of an alcohol containing 6-20 carbon atoms and asuitable saccharide from which excess alcohol has been separated.

Also useful as nonionic surfactants are ethylene oxides condensed withsorbitan fatty acid esters. Such materials are presently commerciallyavailable under the tradename TWEEN (ex. ICI) and/or CRILL (ex. Croda)which include polyoxyethylene sorbitan monolaurate, polyoxyethylenesorbitan monopalmitate, polyoxyethylene sorbitan monostearate,polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitanmonooleate, polyoxyethylene sorbitan trioleates which are available in avariety of grades, and with differing amounts of polyoxylethylene groupsper molecule.

Further useful nonionic surfactants include silicone-containingsurfactants. A preferred class of silicone containing surfactants arethe polyalkylene oxide polysiloxanes having a dimethyl polysiloxanehydrophobic moiety and one or more hydrophilic polyalkylene side chains.

Preferred silicone-containing surfactants include those according to thegeneral formula (1):

R¹—(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)R¹)SiO]_(b)—Si(CH₃)₂—R¹  (1)

wherein (a+b) is about 1 to about 50, specifically about 3 to about 30,more specifically about 10 to about 25, and each R¹ is the same ordifferent and is selected from the group consisting of methyl and apoly(ethyleneoxide/propyleneoxide) copolymer group having the generalformula (2):

—(CH₂)_(n)O(C₂H₄O)_(c)(C₃H₆O)_(d)R²  (2)

with at least one R¹ being a poly(ethyleneoxide/propyleneoxide)copolymer group, and wherein n is 3 or 4; total c (for allpolyalkyleneoxy side groups) has a value of 1 to about 100, preferablyfrom about 6 to about 100; total d is from 0 to about 14, preferablyfrom 0 to about 3; and more preferably d is 0; total c+d has a value offrom about 5 to about 150, preferably from about 9 to about 100 and eachR² is the same or different and is selected from the group consisting ofhydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group,specifically hydrogen and methyl group. In one embodiment, eachpolyalkylene oxide polysiloxane has at least one R¹ group being apoly(ethyleneoxide/propyleneoxide) copolymer group. Examples of thistype of surfactant are the SILWET Hydrostable 68, 611, and 212 (ex.Momentive Performance Materials.)

Non-limiting examples of further surfactants which may be included inthe pressurized, sprayable treatment compositions of the inventioninclude zwitterionic and amphoteric surfactants. Zwitterionicsurfactants may also be present either by themselves or in admixturewith another ionic surfactant providing there are no troublesomeinteractions. Typical examples of amphoteric or zwitterionic surfactantsare alkyl betaines, alkyl amidobetaines, aminopropionates,aminoglycinates, imidazolinium betaines and sulfobetaines. Within thisgroup, alkyl betaines and alkyl amidobetaines are particularlypreferred. Alkyl betaines are known surfactants which are mainlyproduced by carboxyalkylation, preferably carboxymethylation of aminiccompounds. Typical examples are the carboxymethylation products of hexylmethyl amine, hexyl dimethyl amine, octyl dimethyl amine, decyl dimethylamine, dodecyl methyl amine, dodecyl dimethyl amine, dodecyl ethylmethyl amine, C12/14 cocoalkyl dimethyl amine, myristyl dimethyl amine,cetyl dimethyl amine, stearyl dimethyl amine, stearyl ethyl methylamine, oleyl dimethyl amine, C16/18 tallow alkyl dimethyl amine andtechnical mixtures thereof.

Alkyl amidobetaines which represent carboxyalkylation products ofamidoamines are also suitable. Typical examples are reaction products offatty acids containing 6 to 22 carbon atoms, namely caproic acid,caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidicacid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid,arachic acid, gadoleic acid, behenic acid and erucic acid and technicalmixtures thereof, with N,N-dimethylaminoethyl amine,N,N-dimethylaminoproply amine, N,N-diethylaminoethyl amine andN,N-diethylaminoproply amine which are condensed with sodiumchloroacetate. The condensation product of C8/18 cocofattyacid-N,N-dimethylaminopropyl amide with sodium chloroacetate ispreferably used.

Further specific examples of particular amphoteric surfactants which maybe used in the pressurized, sprayable treatment compositions of theinvention include one or more amphoteric surfactants. Exemplaryamphoteric surfactants include alkylampho(mono)acetates,alkylampho(di)acetates, alkylampho(mono)propionates, andalkylampho(di)propionates. Examples of these amphoteric surfactants canbe found under the tradename Miranol from Rhodia (Cranbury, N.J.). Someexamples include Miranol C2M-Conc. NP, described to be disodiumcocoamphodiacetate; Miranol FA-NP, described to be sodiumcocoamphotacetate; Miranol DM, described to be sodium steroamphoacetate;Miranol HMA, described to be sodium lauroamphoacetate; Miranol C2M,described to be cocoamphodiprioponic acid; Miranol C2M-SF, described tobe disodium cocoamphodiproprionate; Miranol CM-SF Conc., described asbeing cocoamphopropriate; Mirataine H2C-HA, described as sodiumlauiminodiproprionate; Miranol Ultra L-32, described as sodiumlauroamphoacetate; and Miranol Ultra C-37, described as sodiumcocoamphoacetate. Other amphoteric surfactants are also available underthe tradename Amphoterge from Lonza (Fair Lawn, N.J.) such as AmphotergeK described to sodium cocoamphoproprionate; Amphoterge K-2, described asdisodium cocoamphodiproprionate; Amphoterge W, described to be sodiumcocoamphoacetate; and Amphoterge W-2, described to be disodiumcocoamphodiacetate.

Further useful amphoteric surfactants include those which may berepresented by the following general formula

in which, R represents a C₄ to C₂₄ alkyl group, and is preferably a C10to C16 alkyl group, R1 and R2 independently represent a C₁ to C₈ alkylgroup, is preferably —CH₂CH₂— or —CH₂CH₂CH₂—, and M may be anysalt-forming anion which permits water solubility or water miscibilityof the compound, e.g., chloride, bromide, methosulfate, ethosulfate,lactate, saccharinate, acetate or phosphate. Such compounds arepresently commercially available, such as those marketed in the TomamineAmphoteric series of amphoteric surfactants, ex. Air Products Inc.

While the one or more detersive surfactants may be present in anyeffective amount which may be observed to improve the microbicidalefficacy of the system of the essential constituents, these one or moresurfactants, when present, are advantageously present in an amount offrom about 0.001-15% wt., preferably from about 0.01-10% wt. andparticularly preferably from about 0.05-5% wt., based on the totalweight of the pressurized, sprayable treatment composition within whichthey are present. In the foregoing amounts, the essential quaternaryammonium compound(s) should not be considered in the weight percentagesof the one or more further optional surfactants, although suchquaternary ammonium compound(s) are often classified as cationicsurfactants. Furthermore, the selection of any one or more furtheroptional surfactants should be made to ensure that it/they do notdeleteriously diminish the microbicidal properties of the essentialquaternary ammonium compound(s) which are essential to the treatmentcompositions of the invention.

The inventive compositions most desirably, although not alwaysessentially, include at least one nonionic surfactant. An example of anespecially preferred nonionic surfactant is at least one alcoholalkoxylate (e.g, ethoxylate, propoxylate) based nonionic surfactant inan amount of from about 0.01-10% wt. In order of increasing preference,when present, the at least one nonionic surfactant comprises in % wt. atleast 0.025, 0.05, 0.075, 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5, 0.6,0.75, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4 and 1.5% wt. and similarly inorder of increasing preference the at least one nonionic surfactantcomprises, in % wt., not more than 10, 9, 8, 7.5, 7, 6, 5, 4.75, 4.5, 4,3.75, 3.5, 3.25, 3, 2.75 and 2% wt. based on the total weight of atreatment composition of which they form a part. In certain embodimentsat least one nonionic surfactant is necessarily present and isconsidered as a further essential constituent of the invention, as it isbelieved that the presence of a nonionic surfactant may advantageouslyimprove the speed and/or degree of control, reduction or elimination ofmicroorganisms. Especially preferred nonionic surfactants and theamounts in which they are preferably present are disclosed in one ormore of the Examples.

In certain embodiments, the sole surfactants present in the compositionsare one or more of the cationic surfactants described above, and/or oneor more of the nonionic surfactants described above.

In certain embodiments the sole surfactant(s) present is one or morecationic surfactants.

In certain embodiments the sole additional surfactant(s) present is oneor more nonionic surfactants.

The pH of the pressurized, sprayable treatment compositions ispreferably established and thereafter maintained at a desired pH orwithin a bounded pH range. A reasonable degree of flexibility informulating compositions of the invention is provided by judiciouscontrol of the pH and the amount of the lower alkyl monohydric alcoholpresent. Specific reference is made to the example formulationsdescribed hereinafter which demonstrate this effect. The pH of theinventive compositions is at least 5, but is preferably greater and incertain particularly preferred embodiments is substantially alkaline.While the pH of the composition may be 5 or greater, preferably the pHof the compositions is at least about 6, and more preferably is in therange of from about 7-14, especially in the range of about 9-12. Thus inpreferred embodiments the pH of the pressurized, sprayable treatmentcompositions (and/or microbicidal control system) is at least 5, and inorder of increasing preference is at least 6, 6.1, 6.2, 6.3, 6.4, 6.5,6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8,8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5,9.6, 9.7, 9.8, 9.9, 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8,10.9, 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12,12.1, 12.2, 12.3, 12.4, 12.5. In preferred embodiments, and in order ofincreasing preference the pH of the pressurized, sprayable treatmentcompositions (and/or microbicidal control system) is not in excess of:12.5, 12.4, 12.3, 12.2, 12.1, 12, 11.9, 11.8, 11.7, 11.6, 11.5, 11.4,11.3, 11.2, 11.1, 11, 10.9, 10.8, 10.7, 10.6, 10.5, 10.4, 10.3, 10.2,10.1, 10, 9.9, 9.8, 9.7, 9.6, 9.5. It is expected that compositions ofthe invention may have lower pHs, in the range of 1-14 if desired;however preferred pHs are indicated in the foregoing ranges and aredemonstrated by the Examples. In certain preferred embodiments the pH ofthe compositions is less than 11. The pH of the pressurized, sprayabletreatment compositions may be established, adjusted and/or maintained bythe addition of an effective amount of a pH adjustment constituent.

Optionally but preferably the pressurized, sprayable treatmentcompositions of the invention include a pH adjusting constituent whichmay be used to establish and/or maintain, viz., buffer, a pressurized,sprayable treatment composition at a desired pH or within a bounded pHrange. As pH adjusting constituents come into consideration essentiallyany material, which may increase or decrease the pH of the pressurized,sprayable treatment composition is suitable as a pH adjustingconstituent. Suitable pH adjusting constituents are one or more acidsand/or bases whether such are based on organic and/or inorganiccompounds or materials. By way of non-limiting example pH adjustingagents include phosphorus containing compounds, monovalent andpolyvalent salts such as of silicates, carbonates, and borates, certainacids and bases, tartrates and certain acetates. Further exemplary pHadjusting agents include mineral acids, basic compositions, and organicacids, which are typically required in only minor amounts. By way offurther non-limiting example pH buffering compositions include thealkali metal phosphates, polyphosphates, pyrophosphates, triphosphates,tetraphosphates, silicates, metasilicates, polysilicates, carbonates,hydroxides, and mixtures of the same. Certain salts, such as thealkaline earth phosphates, carbonates, and hydroxides, can also functionas buffers. It may also be suitable to use as buffers such materials asaluminosilicates (zeolites), borates, aluminates and certain organicmaterials such as gluconates, succinates, maleates, citrates, and theiralkali metal salts. Particularly useful and preferred is citric acid andmetal salts thereof such as sodium citrate which are widely availableand which are effective in providing these pH adjustment and bufferingeffects. Further exemplary and useful pH adjusting constituents includemonoalkanolamines, dialkanolamines, trialkanolamines, andalkylalkanolamines such as alkyl-dialkanolamines, anddialkyl-monoalkanolamines. Such may also function as detersivesurfactants. The alkanol and alkyl groups are generally short to mediumchain length, that is, from 1 to 7 carbons in length. For di- andtrialkanolamines and dialkyl-monoalkanolamines, these groups can becombined on the same amine to produce for example,methylethylhydroxypropylhydroxylamine. One of ordinary skill in the artcan readily ascertain other members of this group. Preferredalkanolamines include monoethanolamine, triethanolamine and the bothmonoethanolamine and triethanolamine. Preferred respective ratios ofmonoethanolamine to triethanolamine are disclosed in the examples.

The use of a citrate as a pH adjusting agent, e.g, sodium citrate, orcitric acid, is preferred, as, while not wishing to be bound by thefollowing, it is hypothesized that the presence of a citrate in thecompositions of the invention facilitate the availability of zinc ionsin the compositions. It is hypothesized that the disassociation of thezinc ions from the zinc ion source material which releases zinc ionsinto the treatment composition into the treatment composition may bereversible reaction, and the concurrent presence of citrates in thecompositions provides for the formation of zinc salts of citrates (or ofcitric acid) which is also believed to be a reversible reaction, but asthe zinc of the zinc salts of the citrates may be more easilydisassociated than the disassociation of zinc from the zinc ion sourcematerial, such may increase the concentration of available free zincions in the composition. Thus, it is preferred that the pH adjustingagent comprise a citrate material (or citric acid), and preferablyfurther, that such be present in at least a molar equivalent or excessof the zinc ion source material. Of course, where the zinc ion sourcematerial includes, or preferably consists of zinc salt of a citrate,such may satisfy this hypothesis.

The control of the pH of the sprayable treatment composition may alsoadvantageously improve the shelf storage stability of pressurizedaerosol canisters containing the sprayable treatment compositions byreducing the likelihood or incidence of corrosion of such canistersparticularly at weld lines, bends or crimp surfaces which are exposed tothe pressurized sprayable treatment compositions. Borate esters, such asmonoethanolamine borate, and monoisopropanolamine borate are examples ofcorrosion inhibitors, although it is to be understood that othermaterials or compositions known to the art, or otherwise disclosed inthis specification may be used in effective amounts.

When present, the one or more pH adjusting constituents are included inamounts which are effective in establishing and/or maintaining the pH ofa pressurized, sprayable treatment composition at or near the desired pHvalue or within a range of pH values. Advantageously the one or more pHadjusting constituents comprise from about 0.001-2.5% wt., preferablyfrom about 0.01-1.5% wt. of the pressurized, sprayable treatmentcomposition of which the one or more pH adjusting constituents form apart. Preferred pH adjusting constituents include those demonstrated inone or more of the Examples. In certain preferred embodiments, one ormore pH adjusting constituents are necessarily present and are to beunderstood as essential constituents of the inventive compositions.

A further optional constituent in the inventive pressurized, sprayabletreatment compositions is one or more chelating agents. Exemplary usefulchelating agents include those known to the art, including by way ofnon-limiting example; aminopolycarboxylic acids and salts thereofwherein the amino nitrogen has attached thereto two or more substituentgroups. Preferred chelating agents include acids and salts, especiallythe sodium and potassium salts of ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid,N-hydroxyethylethylenediaminetriacetic acid, and of which the sodiumsalts of ethylenediaminetetraacetic acid may be particularlyadvantageously used. Such chelating agents may be omitted, or they maybe included in generally minor amounts such as from about 0.001-0.5% wt.based on the weight of the chelating agents and/or salt forms thereof.In certain embodiments, one or more chelating agents are necessarilypresent in the inventive compositions. When present, advantageously,such chelating agents are included in the present inventive compositionin amounts from about 0.001-5% wt., but are most desirably present inreduced weight percentages from about 0.01-0.5% wt. Particularlypreferred corrosion inhibitor constituents and pH adjusting constituentsare disclosed with reference to one or more of the Examples.

As the compositions of the invention are preferably provided inconventional aerosol canisters and may be dispensed therefrom viaconventional aerosol valves, the use of one or more corrosion inhibitorconstituents to limit the corrosion of the aerosol canister may beadvantageous and such may be present in the treatment compositions ineffective amounts. Non-limiting examples of compounds and materialswhich may be used include one or more of phosphates such asmonopotassium phosphate, dipotassium phosphate, tripotassium phosphate,monosodium phosphate, disodium phosphate, ammonium phosphate, nitritessuch as sodium nitrite, ammonium nitrite, ammonium hydroxide, potassiumhydroxide, combinations of triethanolamine with sodium benzoate and/orwith other corrosion inhibitors such as triethanolamine/sodium benzoate,triethanolamine/sodium nitrite, a combination of2-amino-2-methyl-1-propanol and 95% sodium benzoate,tris(hydroxymethyl)aminomethane, borax, combinations of borax withsodium nitrite and/or with other corrosion inhibitors, borate esters, aswell as commercially available preparations such as MONACOR BE, CRODACORBE, AMP-95, HOSTACOR 2732, SANDOCORIN 8160, ELFUGIN AKT Liquid 300, orcombinations thereof. When present, the one or more corrosion inhibitorconstituents are included in amounts which are effective in controllingcan corrosion and/or maintaining the pH of a pressurized, sprayabletreatment composition at the desired pH value or within a range of pHvalues. In certain preferred embodiments, one or more corrosioninhibitor constituents are necessarily present and are essentialconstituents of the invention. Advantageously the one or more corrosioninhibitor constituents comprise from about 0.00001-2.5% wt., preferablyfrom about 0.0001-0.5% wt. of the pressurized, sprayable treatmentcomposition of which the one or more corrosion inhibitor constituentsform a part.

Particular care is to be undertaken in the specification of corrosioninhibitors and/or chelating agents in the inventive compositions. Theinventors have found that excessive amounts of chelating agents and/orcorrosion inhibitors may in some instances undesirably react with orbind with the zinc ions present in the pressurized, sprayable treatmentcompositions thereby reducing their availability as free ions in thesaid compositions.

Similarly, care should be undertaken in the selection of chelatingagents as well, e.g, ethylene diaminetetraacetic acid, which may alsoundesirably reduce the availability of free zinc ions in the saidcompositions. Desirably when such are present they are included in onlylimited amounts so as not to deleteriously affect the improvedmicrobicidal efficacy of the inventive compositions, or chelating agentsmay be excluded from the inventive compositions.

It is to be understood that one or more of the foregoing describedcorrosion inhibitor constituents or pH adjusting constituents mayprovide a dual function and provide both effects.

The sprayable, pressurized inanimate surface treatment compositions ofthe invention may include one or more further optional constituents ormaterials which impart a desired technical and/or aesthetic features ofthe inventive compositions.

The treatment compositions of the invention may optionally include oneor more acids, which include not only organic and inorganic acids butalso acid salts of organic acids. Preferred examples of the organic acidto be used in the present invention include linear aliphatic acids suchas formic acid, acetic acid, propionic acid, butyric acid and valericacid; dicarboxylic acids such as oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, pimelic acid, fumaric acid and maleicacid; acidic amino acids such as glutamic acid and aspartic acid; andhydroxy acids such as glycolic acid, lactic acid, hydroxyacrylic acid,alpha-hydroxybutyric acid, glyceric acid, tartronic acid, malic acid,tartaric acid and citric acid, as well as acid salts of these organicacids. Exemplary inorganic acids include phosphoric acid, potassiumdihydrogenphosphate, sodium dihydrogenphosphate, sodium sulfite,potassium sulfite, sodium pyrosulfite (sodium metabisulfite), potassiumpyrosulfite (potassium metabisulfite), acid sodium hexametaphosphate,acid potassium hexametaphosphate, acid sodium pyrophosphate, acidpotassium pyrophosphate and sulfamic acid. These acids can be usedsingly or as a mixture of two or more inorganic and/or organic acids.Such one or more acids may be used to adjust the pH of the inventivecompositions, and/or buffer the pH of the treatment compositions. Whenpresent, these may be included in effective amounts. Particularly usefulis citric acid and metal salts thereof such as sodium citrate which arewidely available and which are effective in providing these pHadjustment and buffering effects. These should be screened however toensure that they do not undesirably complex with or in other waysdeactivate any quaternary ammonium compound(s) which may be present.

The pressurized, sprayable treatment compositions of the invention mayalso include one or more further compounds, constituents or materialswhich provide an ancillary microbicidal benefit or effect(antimicrobials). These are distinguished from the essentialconstituents of the invention described above. When present, they may beincluded in amounts which are effective in order to provide an ancillarymicrobicidal benefit. Non-limiting examples of such materials includenon-cationic microbicidal agents which are particularly useful in thepresent invention: pyrithiones (especially zinc pyrithione which is alsoknown as ZPT), dimethyldimethylol hydantoin (Glydant),methylchloroisothiazolinone/methylisothiazolinone (Kathon CG), sodiumsulfite, sodium bisulfite, imidazolidinyl urea (Germall 115),diazolidinyl urea (Germaill II), benzyl alcohol,2-bromo-2-nitropropane-1,3-diol (Bronopol), formalin (formaldehyde),iodopropenyl butylcarbamate (Polyphase P100), chloroacetamide,methanamine, methyldibromonitrile glutaronitrile(1,2-Dibromo-2,4-dicyanobutane or Tektamer), glutaraldehyde,5-bromo-5-nitro-1,3-dioxane (Bronidox), phenethyl alcohol,o-phenylphenol/sodium o-phenylphenol, sodium hydroxymethylglycinate(Suttocide A), polymethoxy bicyclic oxazolidine (Nuosept C),dimethoxane, thimersal dichlorobenzyl alcohol, captan, chlorphenenesin,dichlorophene, chlorbutanol, glyceryl laurate, halogenated diphenylethers like 2,4,4-trichloro-2-hydroxy-diphenyl ether (Triclosan or TCS),2,2-dihydroxy-5,5-dibromo-diphenyl ether, phenolic compounds likephenol, 2-methyl phenol. 3-methyl phenol, 4-methyl phenol, 4-ethylphenol, 2,4-dimethyl phenol, 2,5-dimethyl phenol, 3,4-dimethyl phenol,2,6-dimethyl phenol, 4-n-propyl phenol, 4-n-butyl phenol, 4-n-amylphenol. 4-tert-amyl phenol, 4-n-hexyl phenol, 4-n-heptyl phenol, mono-and poly-alkyl and aromatic halophenols such as p-chlorophenol, methylp-chlorophenol, ethyl p-chlorophenol, n-propyl p-chlorophenol, n-butylp-chlorophenol, n-amyl p-chlorophenol, sec-amyl p-chlorophenol, n-hexylp-chlorophenol, cyclohexyl p-chlorophenol, n-heptyl p-chlorophenol,n-octyl p-chlorophenol, o-chlorophenol, methyl o-chlorophenol, ethylo-chlorophenol, n-propyl o-chlorophenol, n-butyl o-chlorophenol, n-amylo-chlorophenol, tert-amyl o-chlorophenol, n-hexyl o-chlorophenol,n-heptyl o-chlorophenol, o-benzyl p-chlorophenol, o-benzyl-m-methylp-chlorophenol, o-benzyl-m, m-dimethyl p-chlorophenol, o-phenylethylp-chlorophenol, o-phenylethyl-m-methyl p-chlorophenol, 3-methylp-chlorophenol, 3,5-dimethyl p-chlorophenol. 6-ethyl-3-methylp-chlorophenol, 6-n-propyl-3-methyl p-chlorophenol,6-iso-propyl-3-methyl p-chlorophenol, 2-ethyl-3,5-dimethylp-chlorophenol. 6-sec-butyl-3-methyl p-chlorophenol,2-iso-propyl-3,5-dimethyl p-chlorophenol, 6-diethylmethyl-3-methylp-chlorophenol, 6-iso-propyl-2-ethyl-3-methyl p-chlorophenol,2-sec-amyl-3,5-dimethyl p-chlorophenol 2-diethylmethyl-3,5-dimethylp-chlorophenol, 6-sec-octyl-3-methyl p-chlorophenol, p-chloro-m-cresol,p-bromophenol, methyl p-bromophenol, ethyl p-bromophenol, n-propylp-bromophenol, n-butyl p-bromophenol, n-amyl p-bromophenol, sec-amylp-bromophenol, n-hexyl p-bromophenol, cyclohexyl p-bromophenol,o-bromophenol, tert-amyl o-bromophenol, n-hexyl o-bromophenol,n-propyl-m,m-dimethyl o-bromophenol, 2-phenyl phenol, 4-chloro-2-methylphenol, 4-chloro-3-methyl phenol, 4-chloro-3,5-dimethyl phenol,2,4-dichloro-3,5-dimethylphenol, 3,4,5,6-terabromo-2-methylphenol,5-methyl-2-pentylphenol, 4-isopropyl-3-methylphenol,para-chloro-meta-xylenol, dichloro meta xylenol, chlorothymol,5-chloro-2-hydroxydiphenylmethane, resorcinol and its derivativesincluding methyl resorcinol, ethyl resorcinol, n-propyl resorcinol,n-butyl resorcinol, n-amyl resorcinol, n-hexyl resorcinol, n-heptylresorcinol, n-octyl resorcinol, n-nonyl resorcinol, phenyl resorcinol,benzyl resorcinol, phenylethyl resorcinol, phenylpropyl resorcinol,p-chlorobenzyl resorcinol, 5-chloro 2,4-dihydroxydiphenyl methane,4-chloro 2,4-dihydroxydiphenyl methane, 5-bromo 2,4-dihydroxydiphenylmethane, and 4-bromo 2,4-dihydroxydiphenyl methane, bisphenoliccompounds like 2,2-methylene bis (4-chlorophenol), 2,2-methylene bis(3,4,6-trichlorophenol), 2,2-methylene bis (4-chloro-6-bromophenol), bis(2-hydroxy-3,5-dichlorophenyl) sulphide, and bis(2-hydroxy-5-chlorobenzyl)sulphide, benzoic esters (parabens) likemethylparaben, propylparaben, butylparaben, ethylparaben,isopropylparaben, isobutylparaben, benzylparaben, sodium methylparaben,and sodium propylparaben, halogenated carbanilides (e.g.,3,4,4-trichlorocarbanilides (Triclocarban or TCC),3-trifluoromethyl-4,4-dichlorocarbanilide, 3,3,4-trichlorocarbanilide,etc.).

Of these, preferred are phenol based non-cationic antimicrobals,especially those based on one or more phenolic compounds, particularly2-hydroxydiphenyl compounds which may be exemplified by the followingclasses of compounds:

wherein Y is chlorine or bromine, Z is SO₂H, NO₂, or C₁-C₄ alkyl, r is 0to 3, o is 0 to 3, p is 0 or 1, m is 0 or 1, and n is 0 or 1. Inpreferred embodiments, Y is chlorine or bromine, m is 0, n is 0 or 1, ois 1 or 2, r is 1 or 2, and p is 0, and according to especiallypreferred embodiments. Y is chlorine, m is 0, n is 0, o is 1, r is 2,and p is 0.

Particularly useful 2-hydroxydiphenyl compounds include those which maybe represented by the structure:

which is commonly referred to as “TRICLOSAN” and which is presentlycommercially available from Ciba Specialty Chemicals Corp., as well ashalogenated carbanilides, e.g., TCC.

Further exemplary useful phenolic based disinfecting agents include2,2′-hydroxy-5,5′-dibromo-diphenyl ether which may be represented by thestructure:

wherein R₁ is hydro, hydroxy, C₁-C₄ alkyl, chloro, nitro, phenyl, orbenzyl; R2 is hydro, hydroxy, C, —C₆ alkyl, or halo; R₃ is hydro, C₁-C₆alkyl, hydroxy, chloro, nitro, or a sulfur in the form of an alkalimetal salt or ammonium salt; R₄ is hydro or methyl, and R₅ is hydro ornitro. Halo is bromo or, preferably, chloro.

Specific examples of phenol derivatives include, but are not limited to,chlorophenols (o-, m-, p-), 2,4-dichlorophenol, p-nitrophenol, picricacid, xylenol, p-chloro-m-xylenol, cresols (o-, m-, p-),p-chloro-m-cresol, pyrocatechol, resorcinol, 4-n-hexylresorcinol,pyrogallol, phloroglucin, carvacrol, thymol, p-chlorothymol,o-phenylphenol, o-benzylphenol, p-chloro-o-benzylphenol, phenol,4-ethylphenol, and 4-phenolsulfonic acid.

Still further useful phenol derivatives include those which may berepresented by the structure:

wherein X is sulfur or a methylene group, R₁ and R′₁ are hydroxy, andR₂, R′₂, R₃, R′₃, R₄, R′₄, R₅, and R′₅, independent of one another, arehydro or halo. Specific, nonlimiting examples of diphenyl compounds arehexachlorophene, tetrachlorophene, dichlorophene,2,3-dihydroxy-5,5′-dichlorodiphenyl sulfide,2,2′-dihydroxy-3,3′,5,5′-tetrachlorodiphenyl sulfide,2,2′-dihydroxy-3,5′,5,5′, 6,6′-hexachlorodiphenyl sulfide, and3,3′-dibromo-5,5′-dichloro-2,2′-dihydroxydiphenylamine. Of theforegoing, a particularly useful phenol derivative is commonly referredto as triclocarban, or 3,4,4′-trichlorocarbanilide as well asderivatives thereto. When present, one or more such further compounds,constituents or materials which provide an ancillary microbicidalbenefit or effect may be present in effective amounts, e.g., in amountsof up to about 5% wt., although depending upon the efficacy of one ormore selected such further compounds, constituents or materials areusually effective in reduced amounts, e.g., 0.001-2% wt. of thetreatment composition.

The pressurized, sprayable treatment compositions of the invention mayoptionally include a fragrance constituent, which may be based onnatural and/or synthetic fragrances and most commonly are mixtures orblends of a plurality of such fragrances, optionally in conjunction witha carrier such as an organic solvent or a mixture of organic solvents inwhich the fragrances are dissolved, suspended or dispersed. Such may benatural fragrances, e.g, natural extracts of plants, fruits, roots,stems, leaves, wood extracts, e.g. terpineols, resins, balsams, animalraw materials, e.g., civet and beaver, as well as typical syntheticperfume compounds which are frequently products of the ester, ether,aldehyde, ketone, alcohol and hydrocarbon type, e.g., benzyl acetate,linalyl acetate, citral, citronellal, methyl cedryl ketone, eugenol,isoeugenol, geraniol, linalool and typically it is preferred to usemixtures of different perfume compounds which, together, produce anagreeable fragrance. Other suitable perfume oils are essential oils ofrelatively low volatility which are mostly used as aroma components.Examples are sage oil, camomile oil, clove oil, melissa oil, mint oil,cinnamon leaf oil, lime-blossom oil, juniper berry oil, vetiver oil,olibanum oil, galbanum oil, labolanum oil and lavendin oil. When presentin a pressurized, sprayable treatment composition, in accordance withcertain of the preferred embodiments, the fragrance constituent may bepresent in any effective amount such that it can be discerned by aconsumer of the composition, however such is advantageously present inamounts of up to about 1% wt., preferably are present in amounts of fromabout 0.00001% wt. to about 0.5% wt., and most preferably is present inan amount of from about 0.0001% wt. to 0.5% wt. based on the totalweight of the treatment composition of which it forms a part.

A further optional constituent of pressurized, sprayable treatmentcompositions of the invention include colorant, such as dyes andpigments which may be used to impart a color to the compositions ofwhich they form a part.

The pressurized, sprayable treatment compositions of the invention mayalso optionally include a preservative constituent which is used tocontrol the undesired presence of microorganisms within the treatmentcomposition which may occur, particularly when the treatment compositionis in long-term storage and/or at elevated temperatures. While these arenormally not present due to the microbicidal efficacy themselves of thecompositions as taught herein, such ancillary preservative constituentsmay be included in minor but effective amounts. Nonlimiting examplesinclude one or more of parabens, including methyl parabens and ethylparabens, glutaraldehyde, formaldehyde,2-bromo-2-nitropropoane-1,3-diol,5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline-3-one,and mixtures thereof. One exemplary composition is a combination5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-onewhere the amount of either component may be present in the mixtureanywhere from 0.001 to 99.99 weight percent, based on the total amountof the preservative. Further exemplary useful preservatives includethose which are commercially including a mixture of5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-onemarketed under the trademark KATHON® CG/ICP as a preservativecomposition presently commercially available from Rohm and Haas(Philadelphia, Pa.). While such preservative composition may be omitted,when present it is advantageously from about 0.00001% wt. to about 0.5%wt., based on the total weight of the treatment composition of which itforms a part.

The pressurized, sprayable treatment compositions of the invention mayinclude one or more further organic solvents, which are differentiatedfrom the essential alkyl aliphatic monohydric alcohol constituent. Suchfurther optional organic solvents may include one or more of: alcoholsother than the essential lower alkyl aliphatic monohydric alcoholdescribed previously, glycols, acetates, ether acetates, glycerols, aswell as polyethylene glycols and glycol ethers. Mixtures of thesefurther optional organic solvents can also be used. Typically suchfurther one or more organic solvents are ones which have no appreciablemicrobicidal effect and are thus differentiated from the essential alkylaliphatic monohydric alcohol constituent. Non-limiting examples ofuseful glycol ethers and examples include those glycol ethers having thegeneral structure R_(a)—O—[CH₂—CH(R)—(CH₂)—O]_(n)—H, wherein R_(a) isC₁₋₂₀ alkyl or alkenyl, or a cyclic alkane group of at least 6 carbonatoms, which may be fully or partially unsaturated or aromatic; n is aninteger from 1 to 10, preferably from 1 to 5; each R is selected from Hor CH₃; and a is the integer 0 or 1. Specific and preferred solvents areselected from propylene glycol methyl ether, dipropylene glycol methylether, tripropylene glycol methyl ether, propylene glycol n-propylether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether,diethylene glycol methyl ether, propylene glycol, ethylene glycol,diethylene glycol monoethyl ether acetate and the like. When presentsuch further optional one or more organic solvents may be present in anyeffective amount, preferably in amounts of between about 0.001-10% wt.,and preferably between about 0.01-5% wt. based on the total weight ofthe treatment composition of which they form a part.

When one or more such further optional constituents are present in thepressurized, sprayable treatment compositions, preferably theircumulative amount does not exceed about 25% wt. and more preferably doesnot exceed about 20% wt., of the treatment composition of which theyform a part.

When one or more such further optional constituents are present in thetreatment compositions, preferably their cumulative amount does notexceed about 25% wt. and preferably does not exceed about 20% wt., ofthe treatment composition of which they form a part.

The inventive compositions, prior to being combined with the propellantconstituent and pressurized, are preferably liquids which have aviscosity in the range of about 100 centipoise (“cP”) or less,preferably and in order of increasing preference, viscosities of about75 cP, 50 cP, 25 cP, 20 cP, 15 cP, 10 cP, 5 cP, 3 cP, 2 cP, and 1 cP,when measured using conventional quantitative method, e.g., as measuredat 20° C. or 25° C. by a Brookfield Type LVT or Type RVT viscometerusing a standard spindle provided by that manufacturer and measuring thesamples at room temperature (20-25° C.).

As the pressurized, sprayable treatment compositions taught herein areused to treat inanimate surfaces including porous and nonporous surfacesand are not provided as a topical skin treatment composition or personalcare composition or for that matter as a wound dressing or a preparationfor use in wound dressings, the treatment compositions most preferablyexclude (unless already described previously) as constituents known-artadditives and adjuvants which are conventional in the cosmetic,pharmaceutical or dermatological field, specifically hydrophilic orlipophilic gelling agents, hydrophilic or lipophilic active agents,humectants, opacifiers, light stabilizers including UV absorbers, andPolyquaternium type polymers which do not provide an antimicrobialbenefit.

The pressurized, sprayable treatment compositions also most preferablyexclude (unless already described previously) thickener componentsespecially one or more of polysaccharide thickeners such as cellulose,alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, naturallyoccurring polysaccharide polymers such as xanthan gum, guar gum, locustbean gum, tragacanth gum, or derivatives thereof, polycarboxylatepolymers, polyacrylamides, clays, and mixtures thereof.

The pressurized, sprayable treatment compositions of the invention areprovided in a pressurized form, and are most preferably packaged or soldas vendible articles in pressured containers, e.g., aerosol canisters.These treatment compositions are desirably dispensed by releasing thecomposition through a manually operated or a power driven motor driven,pressure driven, solenoid driven) actuator or valve, such as aconventional aerosol canister and valve which permits for the egress ofthe contents of the pressurized container via the actuator or valve.Between such dispensing operations however, the contents of such acontainer which includes the treatment composition are pressurized untileither the contents of the pressurized container, viz., the treatmentcomposition have been evacuated, and/or the propellant has beendispensed. Thus a further aspect of the invention provides a pressurizeddispensing container containing the inventive composition as describedherein.

Thus a further aspect of the invention provides a pressurized dispensingcontainer containing the inventive composition as described herein. Suchpressurized, sprayable treatment compositions provided in such a form asa vendible article may be used in the treatment of inanimate surfaces.

As the pressurized, sprayable treatment compositions according to theinvention are most advantageously provided as an “aerosol” type productwherein they are discharged from a pressurized aerosol container, whichuseful pressurized aerosol containers may be based on glass or plasticcontainers, such containers are more advantageously pressurized metalcanisters, especially coated and uncoated steel canisters, which whencoated may be coated with a more corrosion resistant metal such as tinand/or may be provided with a resin, lacquer, plastics or polymericcoating which also improves the corrosion resistance of the containerparticularly when it is pressurized. Aluminum containers areadvantageously used, as well as other metal or metallic containers ormaterials. Any of the forgoing containers may include a resin, lacquer,polymeric or plastics coating which may retard the corrosion of thepressurized canister. If the inventive compositions are used in anaerosol type product, as is strongly preferred, it is preferred thatcorrosion resistant aerosol containers, such as coated or lined aerosolcontainers be used. Such are preferred as they are known to be resistantto the effects of acidic or caustic formulations.

The pressurized, sprayable treatment composition may be dispensed fromthe pressurized dispensing container directly to a surface to betreated. Alternately the pressurized, sprayable treatment compositioncan be dispensed from the pressurized dispensing container onto asubstrate or other article which can then be used to deliver thetreatment composition to a surface to be treated. Preferably suchsubstrates or other articles are porous. Examples of such a substrate orother article include, without limitation, sponges, wipe articles,towels, cloths, pads and the like. Wipe articles can be of a woven ornon-woven nature. Fabric substrates can include nonwoven or wovenpouches, sponges, or in the form of abrasive or non-abrasive cleaningpads. Such fabrics are known commercially in this field and are oftenreferred to as wipes. Such substrates can be resin bonded,hydroentanged, thermally bonded, meltblown, needlepunched or anycombination of the former. Generally, such wipe articles aresubstantially planar in configuration, and have a thickness which ismuch less (generally at least 10 times less, preferably at least 100times less) then the length and/or width of the wipe article. As such,such generally planar wipe articles are typically considered to besubstantially “two-dimensional” type articles.

Nonwoven fabrics may be a combination of wood pulp fibers and textilelength synthetic fibers formed by well known dry-form or wet-layprocesses. Synthetic fibers such as rayon, nylon, orlon and polyester aswell as blends thereof can be employed. The wood pulp fibers shouldcomprise about 30 to about 60 percent by weight of the nonwoven fabric,preferably about 55 to about 60 percent by weight, the remainder beingsynthetic fibers. The wood pulp fibers provide for absorbency, abrasionand soil retention whereas the synthetic fibers provide for substratestrength and resiliency.

The substrate of the wipe may also be a film forming material such as awater soluble polymer. Such self-supporting film substrates may besandwiched between layers of fabric substrates and heat sealed to form auseful substrate. The free standing films can be extruded utilizingstandard equipment to devolatilize the blend. Casting technology can beused to form dry films, or a liquid blend can be saturated into acarrier and then dried in a variety of known methods.

The pressurized, sprayable treatment compositions can also be applied tofoams and sponges, such as open celled or closed celled sponges whichmay be based on naturally occurring or synthetically produced polymers,e.g., hydrophobic polymer sponges such as based on one or morepolyolefins, e.g., polyurethane, as well as hydrophilic polymer foams,e.g. those based on regenerated cellulose, or melamine-formaldehyderesins, as well as natural sponges. The specific type of sponge shouldbe selected to be compatible with the type of pressurized, sprayabletreatment composition with which it will be used.

The treatment compositions of the present invention may be absorbed ontothe wipe to form a saturated wipe and sold as a vendible product. Thewipe can then be sealed individually in a pouch which can then be openedwhen needed or a multitude of wipes can be placed in a container for useon an as-needed basis. The container, when closed, is sufficientlysealed to prevent evaporation of any components from the compositions.Thus a further aspect of the invention provides a closed containercontaining one or more wipes which include the treatment composition asdescribed herein.

The treatment compositions of the invention may be used to provide orimpart a microbicidal effect on treated inanimate surfaces. Preferablythe pressurized, sprayable treatment compositions are characterized inexhibiting a microbicidal benefit when tested against one or morechallenge microorganisms according to one or more of the followingstandardized test protocols: ASTM E1052 Standard Test Method forEfficacy of Antimicrobial Agents against Viruses in Suspension. or ASTME1053 Standard Test Method to Assess Virucidal Activity of ChemicalsIntended for Disinfection of Inanimate, Nonporous EnvironmentalSurfaces, or European Standard Surface Test, EN13697 or AOAC GermicidalSpray Products as Disinfectant Test Method, AOAC Index, 17^(th) Ed.(2000). In particularly preferred embodiments the pressurized, sprayabletreatment compositions exhibit a high degree of microbicidal efficacyagainst various undesirable microorganisms (sometimes referred to as‘pathogens’) including various bacteria, mycobacteria, viruses, andfungi. In particularly preferred embodiments pressurized, sprayabletreatment compositions of the invention exhibit a high degree ofmicrobicidal efficacy against poliovirus type 1 (Sabin) (“PV1”).

The pressurized, sprayable treatment compositions may be applied toinanimate surfaces in order to impart a cleaning effect thereto, butpreferably are applied to impart a microbicidal benefit thereto.Inanimate surfaces include hard surfaces, which are typically nonporoushard surfaces. By way of example, hard surfaces include surfacescomposed of refractory materials such as: glazed and unglazed tile,brick, porcelain, ceramics as well as stone including marble, granite,and other stones surfaces; glass; metals; plastics e.g. polyester,vinyl; fiberglass, Formica®, Corian® and other hard surfaces known tothe industry. Hard surfaces which are to be particularly denoted arelavatory fixtures, lavatory appliances (toilets, bidets, shower stalls,bathtubs and bathing appliances), wall and flooring surfaces especiallythose which include refractory materials and the like. Further hardsurfaces which are particularly denoted are those associated withkitchen environments and other environments associated with foodpreparation. Hard surfaces include those associated with hospitalenvironments, medical laboratories and medical treatment environments.Inanimate surfaces which may be treated by the surface treatmentcompositions of the invention include soft surfaces, non-limitingexamples of which include: carpets, rugs, upholstery, curtains anddrapes, fabrics, textiles, garments, and the like

According to certain embodiments of the invention there are providedprocesses for the treatment of surfaces, including inanimate hardsurfaces and inanimate soft surfaces which process includes the step of:contacting such a surface which is in need of treatment or upon whichthe presence of one or more undesirable microorganisms are suspected orare known to be present, with an effective amount of a treatmentcomposition as described herein to provide a treatment benefit thereto,preferably to provide a microbicidal benefit to the surface,particularly against various undesirable microorganisms (sometimesreferred to as ‘pathogens’) including various bacteria, mycobacteria,viruses, and fungi, and particularly preferably against poliovirus type1 (Sabin) (“PV1”). Such methods require the application of an effectiveamount of a treatment composition as taught herein to such surfaces, sothat the desired microbicidal benefit is imparted to the treatedsurface. Desirably such an effective amount is a sufficient amount of asprayable, pressurized treatment composition which will provide at leasta 1 log₁₀ (log 10) reduction, more preferably at least, and in order ofincreasing preference, a 1.25, 1.5, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25,3.5, 3.75, 4, 4.25, 4.5, 4.75, and 5 log₁₀ reduction (or even higherdegrees of log 10 reduction as disclosed with reference to one or moreof the Examples) against one or more challenge microorganisms, (with thestated log 10 reduction indicated as preferably being beyondcytotoxicity) and preferably against poliovirus type 1 (Sabin) (“PV1”)in accordance with one or more of the testing protocols describedhereinafter, and/or degrees of microbicidal efficacy of poliovirus type1 (Sabin) or other challenge microorganism, as are demonstrated withreference to one or more of the Examples. Preferred embodiments of theinvention provide bactericidal and/or fungicidal and/or mycobactericidaland/or virucidal benefits to treated inanimate surfaces.

With reference to the Examples described later in the tables, thedisclosed compositions were subjected to one or more of the followingtest protocols in order to evaluate their microbicidal efficacy againstone or more of the other challenge microorganisms which are identifiedon Table B. As is known in the art, amongst the most difficult tocontrol or eradicate are viruses, particularly poliovirus type 1(Sabin), and while microbicidal efficacy against the poliovirus type 1(Sabin) presumptively demonstrates that the same composition would beexpected to be effective against the bacteria and the other virusesdisclosed on Table B, the converse is not expected to be true by askilled artisan. Thus, for example, a composition which exhibits goodmicrobicidal efficacy against Gram-positive or Gram-negative bacteria,would not be expected to be particularly effective against thepoliovirus type 1 (Sabin), while the converse would be expected to betrue. Further, even demonstrated efficacy of a composition against arelatively easier to control or eradicate viruses, such as the humanHepatitis A virus, or Human adenovirus, rotaviruses, influenza viruses,herpes simplex type 1 or 2 would not necessarily be expected by askilled artisan to be particularly effective against the poliovirus type1 (Sabin), while the converse would be expected to be true.

Preferred and particularly preferred treatment compositions of theinvention demonstrate a microbicidal benefit when tested according tothe standardized protocol outlined in ASTM E1052 Standard Test Methodfor Efficacy of Antimicrobial Agents against Viruses in Suspension. Thistest is per se, known to the art. Preferred treatment compositionsexhibit a microbicidal benefit against one, but preferably against twoor more of the following challenge organisms, specifically “challenge”viruses: hepatitis A (supplied as hepatitis A virus, strain MH-175 ex.Dr. Mark Sobsey, University of North Carolina, Chapel Hill, N.C.; humanadenovirus type 5 (supplied as ATCC VR-5); feline calicivirus strain F-9(a surrogate for noroviruses) (supplied as ATCC VR-782); herpes simplextype 1 (supplied as ATCC VR-1493); human rhinovirus type 14 strain 1059(supplied as ATCC VR-284), and especially preferably against poliovirustype 1 (Sabin) (supplied by U.S. Centers for Disease Control andPrevention (CDC)), in accordance with this test protocol. As is known tothe skilled artisan, of these forgoing challenge viruses, the mostresistant to control or eradication is the poliovirus type 1 (Sabin) andit is commonly presumed that any composition which shows an effectivedegree of control or eradication against the poliovirus type 1 (Sabin)virus will exhibit an even greater degree of control or eradication ofthe further prior listed viruses. As is known from the literature, e.g.,Hierarchy of susceptibility of viruses to environmental surfacedisinfectants: a predictor of activity against new and emerging viralpathogens. J. AOAC International 90:1655-1658, Sattar, S. A. (2007)),the efficacy of a composition in controlling or eradicating poliovirustype 1 (Sabin) provides an excellent prediction of the composition'sefficacy against further challenge viruses.

Preferred treatment compositions of the invention demonstrate amicrobicidal benefit when tested according to the standardized protocoloutlined in ASTM E1053 Standard Test Method to Assess Virucidal Activityof Chemicals Intended for Disinfection of Inanimate, NonporousEnvironmental Surfaces. This test is also, per se, known to the art.Preferred treatment compositions exhibit a microbicidal benefit againstpoliovirus type 1 (Sabin) (supplied by U.S. Centers for Disease Controland Prevention (CDC)), in accordance with this test protocol. Again, asis known to the skilled artisan, of these forgoing challenge viruses themost resistant to control or eradication is the poliovirus type 1(Sabin) and is it commonly presumed that any composition which shows aneffective degree of control or eradication against the poliovirus type 1(Sabin) will exhibit an even greater degree of control or eradication ofmany other viruses, including adenoviruses, rotaviruses, hepatitis Avirus, feline calicivirus strain F-9 (surrogate for norviruses), herpessimplex type 1 and human rhinovirus type 14 strain 1059 as identifiedabove.

Preferred treatment compositions of the invention demonstrate amicrobicidal benefit when tested according to the standardized protocoloutlined in European Standard Surface Test, EN13697. This test too is,per se, known to the art. Preferred treatment compositions exhibit amicrobicidal benefit against one or more of the following bacteria orfungi: Staphylococcus aureus (supplied as ATCC 6538); Escherichia coli(supplied as ATCC 10536); Pseudomonas aeruginosa (supplied as ATCC15442); Enterococcus hirae (supplied as ATCC 10541) and/or the fungus,Trichophyton mentagrophytes (supplied as ATCC 9533) in accordance withthe protocols of the test.

Certain preferred treatment compositions of the invention alsodemonstrate a microbicidal benefit when tested according to thestandardized protocol identified as the AOAC Germicidal Spray Productsas Disinfectant Test Method, AOAC Index, 17^(th) Ed. (2000). This testis also, per se, known to the art. Preferred treatment compositionsexhibit a microbicidal benefit against one or more of the followingbacteria or fungi: Staphylococcus aureus (“S. aureus” or “Sa”) (suppliedas ATCC 6538); Escherichia coli (“E. coli”, or “Ec”) (supplied as ATCC10536), in accordance with the protocols of the test.

The following examples below illustrate exemplary formulations as wellas preferred embodiments of the invention. It is to be understood thatthese examples are provided by way of illustration only and that furtheruseful formulations falling within the scope of the present inventionand the claims may be readily produced by one of ordinary skill in theart without deviating from the scope and spirit of the invention.

EXAMPLES

A number of treatment compositions as well as a number of comparativecompositions were produced and are described on the following Tables. Inthese identified compositions, the constituents were used “as supplied”from their respective suppliers and may constitute less than 100% wt.“actives”, or may have been supplied as constituting 100% wt. “active”of the named compound, as indicated below. The identified “as supplied”constituent was used, and the “% wt.” of each such constituent isindicated on the tables. Treatment compositions which are considered tofall within the scope of the present invention are identified by a digitprepended with the letter “E” which indicates this to be an “example”composition, while compositions provided only for the purposes ofcomparison are identified by a digit prepended with the letter “C”,which indicates this to be a comparative composition and falling outsideof the scope of the present invention. In certain of the treatmentcompositions, one or more constituents, e.g, a pH adjusting agent, ordeionized water was added in “quantum sufficient” “q.s.” in order toprovide a desired pH or to provide a sufficient mass in order to provide100% wt. of each composition. The example compositions disclosedhereinafter include certain presently preferred embodiments of theinvention. The comparative compositions are presented on Table C, whiletreatment compositions of the invention are identified on one or more ofthe further tables, e.g, Table 1.

The compositions disclosed on the following tables were produced bysimple mixing, under stirring, of the identified constituents, generallyin accordance with the following protocol. To a suitably sizedlaboratory beaker outfitted with a mechanical stirrer or a magneticstirrer, was first supplied a major proportion of the deionized water.All of the constituents, as well as the laboratory beaker were at roomtemperature (approx. 20° C.) and as the beaker was open, mixing was atnormal atmospheric pressure. Thereafter under stirring conditions(approx. 300 rpm) was added the source of zinc ions, and mixingcontinued until this material was dissolved. While stirring continuedwas next added the quaternary ammonium compound(s), and next any pHadjusting agents when such were included. Stirring continued for afurther 15-30 minutes to ensure a homogenous mixture, to which was nextadded the alcohol constituent. Subsequently were added any remainingconstituents including any further quantity of pH adjusting constituents(if present) in order to establish the desired pH of the surfacetreatment composition. Constituents identified as being added “q.s.”were added in order to adjust the pH of the formed composition or tobring the weight of the formed composition to 100% wt. Stirringcontinued for a further 1-15 minutes to ensure the formation of ahomogenous mixture, after which the surface treatment composition waswithdrawn from the beaker and used or tested.

These compositions as identified below were formed using theconstituents identified on the following Table A which identifies thespecific constituents used.

Where not indicated as already incorporating an amount of a suitablepropellant, it is to be understood that to any of the examplecompositions described on the following tables may be added a suitableamount of a propellant. Typically an additional 1-10% wt. of a suitablepropellant may be added to the 100% wt. of an example composition whichcan then be placed into a sealed container or vessel, e.g., an aerosolcanister provided with a dispensing valve, such as a common nozzlethrough which the pressurized treatment composition may be dispensed.

TABLE A Constituents zinc acetate zinc acetate, powder, 100% wt. activezinc sulfate•7H2O zinc sulfate•7H₂O, powder, 100% wt. active zincchloride zinc chloride, powder, 100% wt. active ethanol (100%) ethanol,technical grade, 100% wt. actives BTC-65 (50%) C12-C16 alkyl dimethylbenzyl ammonium chloride provided in an aqueous alcoholic carrier (50%wt. actives) (ex. Stepan) Onyxide 3300 (33%) quaternary ammonium complexwith saccharinate counterion, (33% wt. actives, balance ethanol) (ex.Stepan Co.) Neodol 91-6 nonionic surfactant, C9-C11 linear primaryalcohol ethoxylate, avg. 6 mols. ethoxylation, 100% wt. actives (ex.Shell Chemical) Crodasol WS nonionic surfactant based on alcoholalkoxylates, comprising polyethylene glycol monooctyl ether:CH₃(CH₂)₆CH₂(OCH₂CH₂)_(n)OH where n = 2-8 (100% wt. active) ex. Crodamonoethanolamine monoethanolamine, technical grade (100% wt. active)(ex. Huntsman) triethanolamine triethanolamine, technical grade (100%wt. active) (ex. Dow Chemical Company) sodium citrate•2H2O sodiumcitrate•2H₂O, powder, 100% actives citric acid (anhy.) Anhydrous citricacid, laboratory grade, powder, 100% wt. actives) Citrosol 502(50%)aqueous solution of citric acid (50% wt. active) (ex. ADM) NH4OH(29.86%) aqueous solution of NH4OH (29.6% wt. active) NaOH (10%) aqueoussolution of sodium hydroxide, 10% wt. active Trilon BX aqueous solutionof tetrasodium ethylene diamine tetraacetic acid 38.9% wt. actives) (ex.BASF) Monacor BE borate ester blend, used as supplied (ex. Croda) sodiumbenzoate sodium benzoate, powder, 100% wt. active fragrance fragrance,proprietary composition of its supplier di H2O deionized water, (100%wt. active) propellant 21% wt. n-propane and 79% wt. n-butane, suppliedas “AB46”

It is to be noted that the amount of the “ethanol (100%)” listed in thefollowing tables indicates the amount of ‘neat’ ethanol added as anindividual constituent, but that minor additional amounts of ethanol mayalso be present in the compositions due to the inclusion of one or moreof the foregoing constituents which were supplied with a carrier whichcomprised ethanol, (e.g. Oxyxide 3300, which comprised 66% wt. ethanol),thus in such compositions the total amount of ethanol present isslightly higher than the amount of ‘neat’ ethanol provided as anindividual constituent.

Further, wherein a specific composition was evaluated for microbicidalefficacy against a challenge microorganism according to one or more ofthe test protocols identified above, the results of these tests arereported as well. Wherein multiple challenge microorganisms wereevaluated in any one test, multiple results are reported.

In the following tables, the tested microorganisms and their identity asreported on the tables are as identified on Table B:

TABLE B Microorganisms Identifier Type/Challenge microorganism “PV1”Virus/Poliovirus type 1 Sabin, ex. supplied by U.S. Centers for DiseaseControl and Prevention (CDC) “IV-A” Virus/Influenza A virus,A/California/04/2009 (H1N1), supplied as Biodefence and EmergingInfections Research Resources Repository (BEI Resource) NR-13658 “HAdV”Virus/Human adenovirus type 5, supplied as ATCC VR-5 “FCV” Virus/Felinecalicivirus strain F-9, supplied as ATCC VR-782 “HSV” Virus/Herpessimplex type 1, supplied as ATCC VR-1493 “S. aureus”Bacteria/Staphylococcus aureus, supplied as ATCC or “Sa” 6538 “E. coli”Bacteria/Escherichia coli, supplied as ATCC 10536 or “Ec” “P.aeruginosa” Bacteria/Pseudomonas aeruginosa (“P. aeruginosa”) or “Pa”(supplied as ATCC 15442); “E. hirae”, Bacteria/Enterococcus hirae,supplied as ATCC 10541 or “Eh” “A. niger” Fungus/Aspergillis niger,supplied as ATCC 16404 “T. ment” Fungus/Trichophyton metagropytes,supplied as ATCC 9533 “M. bovis” Pathogen/Mycobacterium tuberculosisvar. bovis

In the following tables, Tables C and CP describes various “comparative”examples, (which comparative examples may be identified by the prependedletter “C”) while subsequent Table 1 and 1P describes various examplesof compositions according to the invention, (which examples may also beidentified by the prepended letter “E”) as well as the observed physicalproperties and the results of microbidical testing according to one ormore of the following standardized test protocols:

A) ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agentsagainst Viruses in Suspension, (for a 5 minute contact time, unlessspecified otherwise) identified on Table 1 as “ASTM E 1052 (log 10reduction)”;B) ASTM E1053 Standard Test Method to Assess Virucidal Activity ofChemicals Intended for Disinfection of Inanimate, NonporousEnvironmental Surfaces, (for a 10 minute contact time, unless specifiedotherwise) identified on Table 1 as “ASTM 1053 (log 10 reduction)”,C) European Standard Surface Test, EN13697, identified on Table 1 as “EN13697 (log 10 reduction)”,D) AOAC Germicidal Spray Products as Disinfectant Test Method, AOACIndex, 17th Ed. (2000), identified on Table 1 as “AOAC GermicidalSpray”. In this test, a result of “0/60” or “1/60” is equivalent to aresult of “pass” according to that test's protocols. Results of “2”excess thereof for “/60” tested plates/samples are considered as beingequivalent to a “fail” according to that test's protocols.E) The European Standard Surface Test, EN13697 protocol (for a 15 minutecontact time, unless specified otherwise) identified on the followingtables as “EN 13697 T. ment” was used for testing antifungal efficacyagainst Trichophyton mentagrophytes or Aspergillis niger; the resultsreported on the tables as the log 10 reduction of the identified fungus.A) ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agentsagainst Viruses in Suspension, (for a 5 minute contact time, unlessspecified otherwise) identified on the following tables as “ASTM E 1052(log 10 reduction)”;B) ASTM E1053 Standard Test Method to Assess Virucidal Activity ofChemicals Intended for Disinfection of Inanimate, NonporousEnvironmental Surfaces, (for a 5 minute contact time, unless specifiedotherwise) identified on the following tables as “ASTM 1053 (log 10reduction)”,C) European Standard Surface Test, EN13697, (for a 5 minute contacttime, unless specified otherwise) identified on the following tables as“EN 13697 (log 10 reduction)”,D) AOAC Germicidal Spray Products as Disinfectant Test Method, AOACIndex, 17th Ed. (2000), (for a 5 minute contact time, unless specifiedotherwise) identified on the following tables as “AOAC GermicidalSpray”. In this test, a result of “0/60” or “1/60” is equivalent to aresult of “pass” according to that test's protocols. Results of “2”excess thereof for “/60” tested plates/samples are considered as beingequivalent to a “fail” according to that test's protocols.E) The European Standard Surface Test, EN13697 protocol (for a 15 minutecontact time, unless specified otherwise) identified on the followingtables as “EN 13697 T. ment” was used for testing antifungal efficacyagainst Trichophyton mentagrophytes or Aspergillis niger; the resultsreported on the tables as the log 10 reduction of the identified fungus.

Table C and Table 1 respectively describe compositions to which apropellant, such as AB46, may be added in a measured amount.

It is noted that each tested composition was not necessarily testedaccording to all of the foregoing protocols as test results ofmicrobicidal efficacy against Poliovirus type 1 Sabin supports thepresumption of efficacy against easier to control or eradicatemicroorganisms.

The inventive compositions disclosed on Table 1 were formulated andtested without the addition of any propellant. The compositions of TableC were comparative examples which were formulated and tested without theaddition of any propellant. The inventive compositions disclosed onTables 1P and 1P-A which included a propellant were pressurized in anaerosol container, and after being dispensed into a clean collectionvessel (which permitted for the propellant to flash off) the remainingdispensed composition retained in the collection vessel was used in theindicated microbicidal testing. The compositions of Table CP disclosedpressurized, comparative example compositions which were prepared andtested as disclosed with reference to the inventive compositionsdisclosed on Tables 1P and 1P-A.

In the following tables the amount of the zinc ions present are alsoindicated in parts per million (ppm) and this number is based on theempirical calculation of the available metal ions present in theindicated composition and 100% disassociation of the zinc ion from thezinc ion source is presumed for this empirical calculation.

In the following tables the appearance of each of the compositions ofTables 1, C, 1P, 1P-A, CP and 2 were essentially colorless andtransparent.

All of the compositions indicated in the following tables were liquidswhich were readily pourable and pumpable and had a “water-thin”viscosity prior to being pressurized (where applicable), as well asafter being dispensed from an aerosol canister (where applicable).

TABLE C (Comparative Compositions) C1 C2 C3 C4 C5 C6 C7 zinc acetate — —— 0.08 — — — zinc sulfate•7H2O — — 0.08 — 0.08 — — zinc chloride — — — —— — — ethanol (100%) 35.0  45.0  — — — — — BTC-65 (50%) — — — — — 0.20 —Onyxide 3300 (33%) — — — — — — 0.30 Neodol 91-6 — — 0.10 — — — —monoethanolamine — — 0.06 — 0.07 — — triethanolamine  0.025  0.005 0.100.07 0.10 —  0.005 sodium citrate•2H2O — — 0.10 0.20 0.10 — — Citrasol502 (50%) — — 0.05 — 0.08 — — NH4OH (29.86%) — — — 0.05 — — — NaOH (10%)— — — — — — — Triton BX — — — — — — — Monacor BE — — — — — — — SilwetHydrostable — — — — — — — fragrance — — — — — — — di H₂O q.s. q.s. q.s.q.s. q.s. q.s. q.s. pH 9.23 8.70 9.03 9.33 9.18 8.58 9.16 zinc ions(ppm) 0   0   182    285    182    0   0   ASTM E 1052 (log10 PV1 = 1.83PV1 = 3.17 PV1 = 2.83 PV1 = 2.17 PV1 = 2.83 PV1 = 1.83 PV1 = 2.50reduction) FCV ≥ 6.00 IVA ≥ 5.00 HSV ≥ 6.00 HAdV = 1.50 ASTM 1053 (log10— — — — — — — reduction) AOAC Germicidal Sa = 60/60 — — — — Sa = 1/60 —Spray Pa = 0/60 Pa = 1/60 EN 13697 (log10 Sa = 4.60 — — — — Sa = 4.47 —reduction) Ec = 4.19 Ec = 4.28 Pa ≥ 4.52 Pa ≥ 4.52 Eh ≥ 6.68 Eh = 3.83EN 13697 T. ment A. niger 0.93 — — — — A. niger 0.85 — (log10 reduction)T. ment 4.84 — — — — T. ment 2.73 — C8 C9 C10 C11 C12 C13 C14 C15 zincacetate 0.08 0.08 — — — — — — zinc sulfate•7H2O — — 0.08 — — — — — zincchloride — — — — — — — — ethanol (100%) — — — 20.0  35.0  45.0  45.0  45.0  BTC-65 (50%) 0.20 0.20 — — 0.20 0.20 — 0.20 Onyxide 3300 (33%) — —0.30 0.30 — — 0.303 — Neodol 91-6 0.10 0.10 — 0.10 0.10 0.10 — 0.10monoethanolamine 0.05 — 0.06 0.05 — — — — triethanolamine — 0.27 0.100.10  0.016 0.01 0.005 — sodium citrate•2H2O — — 0.10 0.08 — — — 0.04Citrasol 502 (50%)  0.012 — 0.06 0.07 — — — — NH4OH (29.86%) — 0.12 — —— — — — NaOH (10%) — — — — — — — — Triton BX — — — — — — — — Monacor BE— — — — — — — — Silwet Hydrostable — — — — — — — — fragrance — — — — — —— — di H₂O q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. pH 8.15 8.66 9.139.05 8.89 7.99 8.03  8.78 zinc ions (ppm) 285    285    182    0   0  0   0    0   ASTM E 1052 (log10 PV1 = 2.17 PV1 = 1.83 PV1 = 2.67 PV1 =2.83 PV1 = 2.17 PV1 = 2.00 PV1 = 2.00 PV1 = 3.00 reduction) ASTM 1053(log10 — — — — — — — — reduction) AOAC Germicidal — — — — — — — — SprayEN 13697 (log10 Sa = 3.90 Sa = 5.01 — — Sa ≥ 6.35 — — — reduction) Ec ≥6.06 Ec ≥ 6.06 Ec ≥ 5.35 Pa ≥ 5.41 Pa ≥ 5.41 Pa ≥ 3.85 Eh ≥ 6.66 Eh ≥6.66 EN 13697 T. ment =1.40  1.09 — — A. niger = — — — (log10 reduction)1.86 C16 C17 C18 zinc acetate — — — zinc sulfate•7H2O — — — zincchloride — — — ethanol (100%) 45.0 55.0  70.0  BTC-65 (50%) — 0.20 —Onyxide 3300 (33%)   0.303 — 0.30 Neodol 91-6 — 0.10 0.10monoethanolamine — 0.06 0.05 triethanolamine  0.03 0.10 0.10 sodiumcitrate•2H2O — 0.10 0.08 Citrasol 502 (50%) — 0.06 0.07 NH4OH (29.86%) —— — NaOH (10%) — — — Triton BX — — — Monacor BE — — — Silwet Hydrostable— — — fragrance — — — di H₂O q.s. q.s. q.s. pH  8.9 9.03 9.14 zinc ions(ppm) 0  0   0   ASTM E 1052 (log10 PV1 = 2.27 PV1 = 4.00 PV1 = 5.83reduction) ASTM 1053 (log10 — — — reduction) AOAC Germicidal — — — SprayEN 13697 (log10 Sa ≥ 6.75 — — reduction) Ec ≥ 6.06 Pa ≥ 5.41 Eh ≥ 6.66EN 13697 T. ment  ≥4.61 — — (log10 reduction)

TABLE 1 (Example Compositions) E1 E2 E3 E4 E5 E6 E7 zinc acetate — —0.08 0.08 0.08 — — zinc sulfate•7H2O 0.10 0.12 — — — 0.12 0.12 zincchloride — — — — — — — ethanol (100%) 20.0  35.0  35.0  35.0  35.0 38.0  38.0  BTC-65 (50%) — — 0.20 0.20 — — — Onyxide 3300 (33%) 0.30 0.303 — — —  0.303  0.303 Neodol 91-6 0.10 0.10 0.10 0.10 0.10 0.100.10 monoethanolamine 0.20 — — 0.74 — — — triethanolamine 0.10 0.15 0.07— 0.07 0.15 — sodium citrate•2H2O 0.08 0.20 0.20 — 0.20 — 0.20 Citrasol502 (50%) 0.32 — — — — 0.09 — NH4OH (29.86%) — 0.17 0.06 — 0.07 0.130.08 NaOH (10%) — — — — — — — Triton BX — — — — — — — Monacor BE — — — —— — — Silwet Hydrostable — — — — — — — fragrance — — — — — — — di H₂Oq.s. q.s. q.s. q.s. q.s. q.s. q.s. pH 9.03 9.50 9.05 10.76  9.11 9.289.46 zinc ions (ppm) 227    272.8   285    285    285    272    272   ASTM E 1052 (log10 PV1 = 2.50 PV1 = 3.30 PV1 = 2.17 PV1 ≥ 5.00 PV1 =2.00 PV1 = 2.33 PV1 = 3.00 reduction) ASTM 1053 (log10 — — — — — — —reduction) AOAC Germicidal — — — — — — — Spray EN 13697 (log10 — — Sa ≥6.75 — Sa ≥ 6.75 — — reduction) Ec ≥ 6.06 Ec ≥ 6.06 Pa ≥ 5.41 Pa ≥ 5.41Eh ≥ 6.66 Eh ≥ 6.66 EN 13697 T. ment — — ≥4.61   — ≥4.61   — — (log10reduction) E8 E9 E10 E11 E12 E13 E14 zinc acetate — — — — — — — zincsulfate•7H2O 0.08 0.08 0.08 0.08 0.08 0.08 0.08 zinc chloride — — — — —— — ethanol (100%) 40.0  40.0  40.0  40.0  40.0  40.0  40.0  BTC-65(50%) — — — — — — — Onyxide 3300 (33%) — —  0.300 0.30 0.15 0.15 0.30Neodol 91-6 — 0.10 0.10 0.10 0.10 0.10 0.10 monoethanolamine 0.06 0.07 0.008  0.015 0.06 0.80 0.70 triethanolamine 0.10 0.10 0.10 0.10 0.100.10 0.10 sodium citrate•2H2O 0.10 0.10 0.20 0.20 0.10 0.10 0.20Citrasol 502 (50%) 0.05 0.05  0.015 — 0.05 0.05 — NH4OH (29.86%) — — — —— 0.08 0.15 NaOH (10%) — — — — — — — Triton BX — — — — — — — Monacor BE— — — — — — — Silwet Hydrostable — — — — — — — fragrance — — — — — — —di H₂O q.s. q.s. q.s. q.s. q.s. q.s. q.s. pH 9.00 9.13 8.52 9.13 9.0510.73  11.0  zinc ions (ppm) 182    182    182    182    182    182   182    ASTM E 1052 (log10 PV1 = 2.56 PV1 = 2.73 PV1 = 2.50 PV1 = 2.83PV1 = 3.00 PV1 ≥ 6.00 PV1 ≥ 5.00 reduction) ASTM 1053 (log10 — — — — — —— reduction) AOAC Germicidal — — — — — — — Spray EN 13697 (log10 — — Sa≥ 6.75 — — — — reduction) Ec ≥ 6.06 Pa ≥ 5.41 Eh ≥ 6.66 EN 13697 T. ment— — ≥4.61   — — — — (log10 reduction) E15 E16 E17 E18 E19 E20 E21 E22zinc citrate•3H2O 0.10 0.10 — — — — — 0.15 zinc sulfate•7H2O — —  0.115 0.115  0.115 0.12 0.12 — zinc chloride — — — — — — — — ethanol (100%)40.0  40.0  40.0  40.0  40.0  40.0  43.0  40.0  BTC-65 (50%) 0.40 0.40 —— — — — 0.20 Onyxide 3300 (33%) — —  0.303 0.91 0.30 0.30  0.303 —Neodol 91-6 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 monoethanolamine — —— 0.20 0.41 0.04 — — triethanolamine 0.34 0.38 0.72 0.38 0.38 0.10 0.150.38 sodium citrate•2H2O — — — — — 0.20 — — Citrasol 502 (50%) 0.07 0.070.15 0.19 0.19 — 0.02 0.08 NH4OH (29.86%) — 0.15 — 0.08 0.07 — 0.12 —NaOH (10%) — 0.45 — 0.25 0.42 — — — Triton BX — — — — — — — — Monacor BE— — — — — — — — Silwet Hydrostable — — — — — — — — fragrance — — — — — —— — di H₂O q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. pH 7.92 11.02  7.929.72 10.35  9.10 9.46 7.89 zinc ions (ppm) 310    310    261    261   261    272.8   272.8   465    ASTM E 1052 (log10 PV1 = 2.00 PV1 ≥ 5.00PV1 = 2.50 PV1 ≥ 4.73 PV1 ≥ 5.00 PV1 = 2.17 PV1 = 3.92 PV1 = 2.00reduction) ASTM 1053 (log10 — — — — — — — — reduction) AOAC Germicidal —— — — — — — — Spray EN 13697 (log10 — — — — — — — — reduction) EN 13697T. ment — — — — — — — — (log10 reduction) E23 E24 E25 E26 E27 E28 E29E30 zinc acetate — 0.08 0.08 0.08 — — 0.08 0.08 zinc sulfate•7H2O 0.12 —— — — — — — zinc chloride — — — —  0.055  0.055 — — ethanol (100%) 43.0 45.0  45.0  45.0  45.0   45.0  45.0  45.0  BTC-65 (50%) — — — — — — — —Onyxide 3300 (33%)  0.303 — —  0.303  0.303  0.303  0.303  0.303 Neodol91-6 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 monoethanolamine — — 0.02 —— — — — triethanolamine 0.15 0.12 0.27 0.22 0.38 0.38 0.22  0.295 sodiumcitrate•2H2O — 0.20 — — — — — — Citrasol 502 (50%) 0.02 — 0.14 0.27 0.150.12  0.145 0.13 NH4OH (29.86%) 0.12 0.03 0.12 — 0.30 0.30 0.15 0.26NaOH (10%) — — — — — — — — Triton BX — — — — — — — — Monacor BE — — — —— 0.10 0.06 — Silwet Hydrostable — — — — — — — — fragrance — — — — — — —— di H₂O q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. pH 9.46 8.05 8.74 6.078.34 9.27 9.25 9.45 zinc ions (ppm) 272.8   285    285    285   263.8  263.8   285    285    ASTM E 1052 (log10 PV1 = 3.92 PV1 = 2.50 PV1 ≥5.00 PV1 = 1.25 PV1 = 2.27 PV1 ≥ 4.73 PV1 ≥ 5.00 PV1 = 4.50 reduction)ASTM 1053 (log10 — — — — — — — — reduction) AOAC Germicidal — — — — — —Sa = 0/30 — Spray Pa = 0/30 EN 13697 (log10 — — Sa ≥ 6.75 — — — Sa ≥6.75 — reduction) Ec ≥ 6.06 Ec ≥ 6.06 Pa ≥ 5.41 Pa ≥ 5.41 Eh ≥ 6.66 Eh ≥6.66 EN 13697 T. ment — — ≥4.61   — — — ≥4.61   — (log10 reduction) E31E32 E33 E34 E35 E36 E37 E38 zinc acetate 0.08 0.08 0.08 0.08 0.08 0.080.08 0.08 zinc sulfate•7H2O — — — — — — — — zinc chloride — — — — — — —— ethanol (100%) 45.0  45.0  45.0  45.0  45.0  45.0  45.0  45.0  BTC-65(50%) — 0.20 0.20 0.20 — — — 0.20 Onyxide 3300 (33%) — — — — —  0.303 0.303 — Neodol 91-6 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10monoethanolamine — — — — 0.02 0.11 0.11 0.75 triethanolamine 0.12 0.270.22  0.335 0.27 0.22 0.22 0.07 sodium citrate•2H2O 0.20 — — — — — —0.20 Citrasol 502 (50%) — 0.14 0.21 — 0.14  0.155 0.14 — NH4OH (29.86%)0.03 0.08 0.14 — 0.12  0.124  0.124 0.17 NaOH (10%) — — — — — — — —Triton BX — — — 0.26 — — — — Monacor BE — — — — — 0.08 — — SilwetHydrostable — — — — — — — — fragrance — — — — — — — — di H₂O q.s. q.s.q.s. q.s. q.s. q.s. q.s. q.s. pH 8.05 8.09 8.56 8.6  8.74 9.63 9.6310.78  zinc ions (ppm) 285    285    285    285    285    285    285   285    ASTM E 1052 (log10 PV1 = 2.50 PV1 = 3.50 PV1 = 3.83 PV1 ≥ 5.50PV1 ≥ 5.00 PV1 ≥ 4.50 PV1 ≥ 4.50 PV1 ≥ 5.00 reduction) ASTM 1053 (log10— — — — — — — — reduction) AOAC Germicidal — — — — — — — — Spray EN13697 (log10 — — Sa ≥ 6.75 — Sa ≥ 6.75 — — — reduction) Ec = 4.98 Ec ≥6.06 Pa ≥ 5.41 Pa ≥ 5.41 Eh ≥ 6.66 Eh ≥ 6.66 EN 13697 T. ment — —≥4.61   — ≥4.61   — — — (log10 reduction) E39 E40 E41 E42 E43 zincacetate 0.08 — — — — zinc sulfate•7H2O — 0.10 0.10  0.115  0.115 zincchloride — — — — — ethanol (100%) 45.0  55.0  70.0  45.0  45.0  BTC-65(50%) — 0.20 — — — Onyxide 3300 (33%)  0.303 — 0.30  0.303 0.30 Neodol91-6 0.10 0.10 0.10 0.10 0.10 monoethanolamine —  0.075 0.15 — 0.20triethanolamine 0.27 0.10 0.10 0.35 0.40 sodium citrate•2H2O — 0.10 0.08— — Citrasol 502 (50%) 0.14 0.06 0.20 0.14 0.19 NH4OH (29.86%) — — —0.09 0.13 NaOH (10%) — — — — — Triton BX — — — — — MEA-MIPA borate — — —— — Monacor BE — — — — — Silwet Hydrostable — — — — — fragrance — — — —— di H₂O q.s. q.s. q.s. q.s. q.s. pH 7.08 9.03 9.2  8.14 9.5  zinc ions(ppm) 285    227.4   227.4   261    261    ASTM E 1052 (log10 PV1 ≥ 3.17PV1 = 4.17 PV1 ≥ 6.00 PV1 = 1.50 PV1 ≥ 4.73 reduction) ASTM 1053 (log10— — — — — reduction) AOAC Germicidal — — — — — Spray EN 13697 (log10 — —— — — reduction) EN 13697 T. ment — — — — — (log10 reduction) E44 E45E46 E47 E48 E49 E50 zinc acetate — — — — — — — zinc sulfate•7H₂O 0.130.13 0.13 0.13 0.13 0.13 0.13 zinc chloride — — — — — — — ethanol (100%)43.0  43.0  43.0  43.0  43.0  43.0  43.0  BTC-65 (50%) — — — — — — —Onyxide 3300 (33%) 0.33 0.33 0.33 0.33 0.33 0.33 0.33 Neodol 91-6 0.100.10 0.10 0.10 0.10 0.10 0.10 monoethanolamine 1.04 1.04 1.04 1.04 1.041.04 1.04 triethanolamine 0.10 0.10 0.10 0.10 0.10 0.10 0.10 sodiumcitrate — — — — — — — Citrasol 502 (50%) 0.12 0.12 0.12 0.12 0.12 0.120.12 NH4OH (29.86%) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 NaOH (10%) — — —— — — — Triton BX — — — — — — — Monacor BE  0.065 0.10 0.15 0.25 — — —sodium benzoate — — — — 0.06 0.10 0.15 Silwet Hydrostable — — — — — — —fragrance — — — — — — — di H₂O q.s. q.s. q.s. q.s. q.s. q.s. q.s. pH10.55  10.54  10.52  10.45  10.58  10.55  10.51  zinc ions (ppm) — — — —— — — ASTM E 1052 (log10 PV1 ≥ 7.00 PV1 ≥ 7.00 PV1 ≥ 7.00 PV1 ≥ 7.00 PV1≥ 7.00 PV1 ≥ 7.00 PV1 ≥ 7.00 reduction) ASTM 1053 (log10 — — — — — — —reduction) AOAC Germicidal — — — — — — — Spray EN 13697 (log10 — — — — —— — reduction) EN 13697 T. ment — — — — — — — (log10 reduction)

Any of the compositions described on Table 1 may also be formed into apressurized surface treatment composition of the invention by theaddition of a further, suitable amount of a propellant thereto.Particularly preferred forms of the pressurized surface treatmentcompositions are ones in which between about 80-99.5 parts by weight ofan inventive treatment composition indicated on Table 1, and identifiedwith the prepended letter “E” (e.g. “E1”, “E2” etc.) are combined with0.5-20 parts by weight of suitable propellant or propellant composition,and the resultant blend or mixture is supplied to a sealable dispensingcontainer, such as an aerosol canister which includes a valve whichpermits for the sprayable, pressurized treatment compositions to exitthe container. Typically such a sealed dispensing container includes inaddition to the valve, a valve stem upon which is mounted a conventionalspray nozzle adapted to be compressed or tilted by a consumer in orderto release the pressurized composition as an aerosol. For example, aquantity of a composition according to the invention as described onTable 1 is supplied to a suitable aerosol canister, to which is added,e.g., 7% vol. of a propellant composition and the aerosol canister issealed. The sprayable treatment composition may be dispensed from theaerosol canister in a conventional manner and used to treat an inanimatesurface.

As can be seen from the foregoing results, the compositions of theinvention exhibited excellent microbicidal efficacy as demonstrated bythe various test results, even wherein reduced amounts of ethanol waspresent as a constituent. In the foregoing compositions of Table C andTable 1, a propellant constituent was omitted, however may have beenadditionally added, e.g, in any additional amount of about 0.5-20% wt.,based on the compositions of Table 1, in order to produce compositionsaccording to the invention. The foregoing tables demonstrate theantimicrobial efficacy of the indicated compositions, it beingunderstood that had a propellant been added and the compositionpressurized in an aerosol canister, the dispensed and recoveredcomposition would be substantially as described as disclosed in Table Cor Table 1 after the propellant was flashed off from the dispensedcomposition.

The following table CP provides several comparative pressurizedcompositions, while tables 1P and 1P-A demonstrate pressurizedcompositions of the invention.

TABLE CP (Pressurized, Comparative Examples) C19 C20 C21 C22 zincacetate — — — — zinc sulfate•7H2O — — 0.13 — zinc chloride — — — —ethanol (100%) 37.20  39.06  — 44.22  BTC-65 (50%) — — — — Onyxide 3300(33%) 0.30  0.30  — 0.313 Crodasol WS — — 0.14 0.14  Neodol 91-6 0.0930.093 — — monoethanolamine 0.223 0.707 0.97 0.97  triethanolamine 0.0930.093  0.093 0.093 sodium citrate•2H₂O — — — — Citric acid (anhy.) — — 0.056 0.056 Citrasol 502 (50%) 0.11  0.11  — — NH4(OH) (29.86%) 0.0930.093  0.093 0.093 NaOH (10%) — — — — Triton BX — — — — Monacor BE — —0.14 0.14  Silwet Hydrostable — — — — fragrance — — — 0.225 propellant7.0  7.0  7.0  7.0  di H₂O q.s. q.s. q.s. q.s. pH 10.04  10.47  10.60 10.54  zinc ions (ppm) 0    0    295.1   0    can type W W S S ASTM E1052 (log10 — — — — reduction) ASTM 1053 (log10 PV1 = 3.00 PV1 = 3.58 —— reduction) AOAC Germicidal — — Sa = 30/30 Sa = 0/30 Spray Pa = 5/30 Pa= 0/60 EN 13697 (log10 — — — — reduction) EN 13697 T. ment — — — —(log10 reduction) C23 C24 C25 C26 C27 C28 zinc acetate — — — — — — zincsulfate•7H₂O — — — — — — zinc chloride — — — — — — ethanol (100%) 49.77 49.77  49.77  49.77  49.77  49.77  BTC-65 (50%) — — — — — — Onyxide 3300(33%)  0.337  0.337  0.337  0.337  0.337  0.337 Neodol 91-6 — — — — — —monoethanolamine 0.02 — — 0.13 0.65 2.51 triethanolamine 0.1  0.1  0.1 0.1  0.1  0.1  sodium citrate•2H₂O — — — — — — Citrasol 502 (50%) 0.350.26 0.19 0.12 0.12 0.12 NH4(OH) (29.86%) 0.1  0.1  0.1  0.1  0.1  0.1 NaOH (10%) — — — — — — Trilon BX — — — — — — Monacor BE 0.15 0.15 0.150.15 0.15 0.15 Crodasol WS 0.15 0.15 0.15 0.15 0.15 0.15 fragrance — — —— — — di H₂O q.s. q.s. q.s. q.s. q.s. q.s. pH 9.0  9.25 9.53 10.0  10.5 10.99  zinc ions (ppm) 0   0   0   0   0   0   can type S S S S S S ASTM1053 (log10 — — — PV1 = 0.73 PV1 = 0.90 PV1 = 090 reduction), 30 secondscontact time ASTM 1053 (log10 — — — — — PV1 = 2.23 reduction), 5 minutescontact time To each of comparative examples C23 through C28 was addedan additional amount of 10% wt. of AB46 (based on the total weight ofthe remaining constituents, which totaled 100% wt.) as the propellantconstituent, and the reported microbicidal testing was performedutilizing the recovered liquid collected immediately after a quantity ofthe pressurized composition was dispensed from an aerosol canister

TABLE 1P (Pressurized, Example Compositions) E51 E52 E53 E54 E55 E56 E57zinc acetate — — — — — — — zinc sulfate•7H₂O 0.12  0.116  0.116  0.1160.12 0.12 0.12  zinc chloride — — — — — — — ethanol (100%) 33.95  38.8 38.8  43.65  37.20  37.20  37.20  BTC-65 (50%) — — — — — — — Onyxide3300 (33%) 0.30 0.29 0.29 0.29 0.30 0.30 0.30  Neodol 91-6  0.093 0.090.09 0.09  0.093  0.093 0.093 monoethanolamine — — 0.25 — 0.13 0.440.837 triethanolamine 0.13 0.12 0.12 0.12  0.093  0.093 0.093 sodiumcitrate•2H₂O 0.18 0.18 0.18 0.18 — — — Citrasol 502 (50%) — — — —  0.093 0.093 0.093 NH4OH (29.86%)  0.081  0.081 0.14  0.063 0.11 0.11 0.11 NaOH (10%) — — — — — — — Triton BX — — — — — — — Monacor BE — — — — — —— Silwet Hydrostable — — — — — — — fragrance — — — — — — — propellant7.0  7.0  7.0  7.0  7.0  7.0  7.0  di H₂O q.s. q.s. q.s. q.s. q.s. q.s.q.s. pH 9.11 9.17 10.44  9.18 9.45 9.98 10.37  zinc ions (ppm) 272.8  272.8   272.8   272.8   272.8   272.8   272.8   can type W W W W W W WASTM E 1052 (log10 PV1 = 1.73 PV1 = 3.27 PV1 ≥ 5.00 PV1 ≥ 5.00 — PV1 ≥5.00 — reduction) ASTM 1053 (log10 PV1 = 0.00 PV1 = 0.38 PV1 ≥ 2.25 PV1= 2.00 PV1 = 2.28 PV1 ≥ 4.25 PV1 ≥ 4.50 reduction) AOAC Germicidal — — —— — — — Spray EN 13697 (log10 — — — — — — — reduction) EN 13697 T. ment— — — — — — — (log10 reduction) E58 E59 E60 E61 E62 zinc acetate — — — —— zinc sulfate•7H₂O 0.12 0.12 0.12  0.12 0.12  zinc chloride — — — — —ethanol (100%) 39.06  39.06  39.06  39.06  41.85  BTC-65 (50%) — — — — —Onyxide 3300 (33%) 0.30 0.30 0.30  0.30 0.30  Neodol 91-6  0.093  0.0930.093  0.093 0.093 monoethanolamine 0.13 0.44 0.065  0.809 0.186triethanolamine  0.093  0.093 0.093  0.093 0.093 sodium citrate•2H₂O — —0.186 — — Citrasol 502 (50%) 0.11 0.11 — 0.11 0.11  NH4OH (29.86%) 0.110.11 0.11  0.11 0.102 NaOH (10%) — — — — — Triton BX — — — — — MonacorBE — — — — — Silwet Hydrostable — — — — — fragrance — — — — — propellant7.0  7.0  7.0  7.0  7.0  di H₂O q.s. q.s. q.s. q.s. q.s. pH 9.40 9.9510.13  10.38  9.33  zinc ions (ppm) 272.8   272.8   272.8   272.8  272.8   can type W W W W W ASTM E 1052 (log10 PV1 ≥ 5.00 PV1 ≥ 5.00 PV1≥ 5.00 PV1 ≥ 5.00 — reduction) ASTM 1053 (log10 PV1 = 4.75 PV1 ≥ 5.00PV1 = 4.00 PV1 ≥ 4.42 PV1 = 3.05 reduction) AOAC Germicidal — — — — —Spray EN 13697 (log10 — — — — — reduction) EN 13697 T. ment — — — — —(log10 reduction) E63 E64 E65 E66 zinc acetate — — — — zinc sulfate•7H₂O0.12 0.12  0.12  0.12 zinc chloride — — — — ethanol (100%) 41.85  41.85 40.0   39.81  BTC-65 (50%) — — — — Onyxide 3300 (33%) 0.30 0.30  0.30 0.30 Neodol 91-6  0.093 0.093 0.093  0.093 monoethanolamine  0.502 0.8180.931 0.26 triethanolamine  0.093 0.093 0.093 0.12 sodium citrate•2H₂O —— — — Citrasol 502 (50%) 0.11 0.11  0.12  — NH4OH (29.86%)  0.093 0.0930.093 0.15 NaOH (10%) — — — — Triton BX — — — — Monacor BE — — — —Silwet Hydrostable — — — 0.10 fragrance — — — — propellant 7.0  7.0 7.0  7.0  di H₂O q.s. q.s. q.s q.s. pH 9.98 10.25  10.50  10.50  zincions (ppm) 272.8   272.8   272.8   272.8   can type W W S E ASTM E 1052(log10 — — PV1 ≥ 7.00 PV1 ≥ 7.00 reduction) ASTM 1053 (log10 PV1 = 4.58PV1 ≥ 5.00 PV1 ≥ 5.00 PV1 ≥ 4.5 reduction) (10 min) (10 min) AOACGermicidal — — — — Spray EN 13697 (log10 — — — — reduction) EN 13697 T.ment — — — — (log10 reduction)

TABLE 1 E67 E68 E69 E70 E71 E72 E73 zinc acetate — — — — — — — zincsulfate•7H₂O 0.126 0.126  0.0099  0.0198 0.198  0.3869 3.969 zincchloride — — — — — — — ethanol (100%) 42.80  42.797  42.797  42.797 42.797  42.797  42.797  BTC-65 (50%) — — — — — — — Onyxide 3300 (33%)0.303 0.303 0.303 0.303 0.303 0.303 0.303 Neodol 91-6 — — — — — — —Crodasol WS 0.135 0.135 0.135 0.135 0.135 0.135 0.135 monoethanolamine0.936 0.936 0.936 0.936 1.362 2.382 11.937  triethanolamine 0.09  0.09 0.09  0.09  0.09  0.09  0.09  citric acid (anhy.) 0.054 0.10  0.0080.015 0.157 0.315 3.15  sodium citrate•2H₂O — — — — — — — Citrasol 502(50%) — — — — — — — NH4OH (29.86%) 0.09  0.09  0.09  0.09  0.09  0.09 0.09  NaOH (10%) — — — — — — — Triton BX — — — — — — — Monacor BE 0.1350.135 0.135 0.135 0.135 0.135 0.135 Silwet Hydrostable — — — — — — —fragrance 0.218 0.218 — — — — — di H₂O q.s. q.s. q.s. q.s. q.s. q.s.q.s. pH 10.50  10.45  10.73  10.66  10.26  10.54  10.08  zinc ions (ppm)286     286     22.5   45    450     900     9000     ASTM E 1052 (log10— — — — — — — reduction) ASTM 1053 (log10 PV1 ≥ 4.75 PV1 ≥ 4.25 PV1 ≥5.83 PV1 ≥ 5.83 PV1 ≥ 5.83 PV1 ≥ 5.83 PV1 ≥ 5.83 reduction) AOACGermicidal — — — — — — — Spray, 5 minute contact time EN 13697 (log10 —— — — — — — reduction) EN 13697 T. ment — — — — — — — (log10 reduction)E74 E75 E76 E77 E78 E79 E80 zinc acetate — — — — — — — zinc sulfate•7H₂O  0.0003969  0.00198  0.00396  0.00594  0.00792 0.126 0.126 zincchloride — — — — — — — ethanol (100%) 42.797  42.797  42.797  42.797 42.797  49.797  46.797  BTC-65 (50%) — — — — — — — Onyxide 3300 (33%)0.303 0.303 0.303 0.303 0.303 0.303 0.303 Neodol 91-6 — — — — — — —Crodasol WS 0.135 0.135 0.135 0.135 0.135 0.135 0.135 monoethanolamine0.950 1.073 1.026 1.284 1.233 1.47  0.936 triethanolamine 0.090 0.0900.090 0.090 0.090 0.090 0.090 citric acid (anhy.) 0.100 0.100 0.1000.100 0.100 0.100 0.100 sodium citrate•2H₂O — — — — — — — Citrasol 502(50%) — — — — — — — NH4OH (29.86%) 0.09  0.09  0.09  0.09  0.09  0.09 0.09  NaOH (10%) — — — — — — — Triton BX — — — — — — — Monacor BE 0.1350.135 0.135 0.135 0.135 0.135 0.135 Silwet Hydrostable — — — — — — —fragrance — — — — — 0.225 0.225 di H₂O q.s. q.s. q.s. q.s. q.s. q.s.q.s. pH 10.47  10.52  10.45  10.53  10.43  10.68  10.43  zinc ions (ppm)0.9  4.5  9    13.5   18    286     286     ASTM E 1052 (log10 — — — — —— — reduction) ASTM 1053 (log10 PV1 = 2.90 PV1 = 3.23 PV1 = 3.23 PV1 =3.56 PV1 = 4.23 PV1 ≥ 4.27 PV1 ≥ 4.27 reduction) AOAC Germicidal — — — —— — — Spray, 5 minute contact time EN 13697 (log10 — — — — — — —reduction) EN 13697 T. ment — — — — — — — (log10 reduction)

The compositions of Table 1P and Table CP, which as indicated, included7% wt. of the propellant, AB46, and were supplied to one or more typesof conventional, sealed dispensing container which are defined in thosetables as “can type” wherein:

can type: S unlined tin-plated, three-piece steel can, nominal 6 fluidounce fill volume (ex. Ball Co.) E epoxy phenolic lined aluminum can,nominal 500 ml fill volume (ex. EXAL Co.) W polymer lined, transparentglass Wheaton bottle, nominal 120 ml fill volume

Each of the foregoing sealed dispensing containers further comprised avalve which permitted for the dispensing of the sprayable, pressurizedtreatment compositions. The sprayable treatment composition wasdispensed in a conventional manner and used for subsequent testing,viz., by releasing it from the container, and then evaluated accordingto one or more of the tests indicated on the Tables.

As can be seen from the foregoing results indicated on the foregoingTables, the compositions of the invention exhibited excellentmicrobicidal efficacy as demonstrated by the various test results, evenwherein reduced levels of ethanol (e.g, less than 50% wt, especially 45%wt.) were present as a constituent.

Further examples of sprayable, pressurized inanimate surface treatmentcompositions according to the invention are described on Table 1P-Awhich incorporated slightly higher amounts of the propellant, AB46. Theindicated proportion of the composition of Table 1P-A was combined withthe AB46 propellant, in a unlined tin-plated, three-piece steel can,nominal 6 fluid ounce fill volume (ex. Ball Co.) (can type: “S”) to forma pressurized composition. Subsequently the sprayable, pressurizedinanimate surface treatment compositions were dispensed from the caninto a clean glass beaker, and the collected liquid was used in thesubsequent microbicidal testing.

TABLE 1P-A E98 E99 E100 E101 E102 E103 zinc acetate — — — — — — zincsulfate•7H₂O 0.14 0.14 0.14 0.14 0.14 0.14 zinc chloride — — — — — —ethanol (100%) 49.77  49.77  49.77  49.77  49.77  49.77  BTC-65 (50%) —— — — — — Onyxide 3300 (33%)  0.337  0.337  0.337  0.337  0.337  0.337Neodol 91-6 — — — — — — monoethanolamine — 0.01 — 0.34 1.4  4.92triethanolamine 0.1  0.1  0.1  0.1  0.1  0.1  sodium citrate•2H₂O — — —— — — Citrasol 502 (50%) 0.27 0.18 0.12 0.12 0.12 0.12 NH4(OH) (29.86%)0.1  0.1  0.1  0.1  0.1  0.1  NaOH (10%) — — — — — — Trilon BX — — — — —— Monacor BE 0.15 0.15 0.15 0.15 0.15 0.15 Crodasol WS 0.15 0.15 0.150.15 0.15 0.15 fragrance — — — — — — di H₂O q.s. q.s. q.s. q.s. q.s.q.s. pH 9.0  9.25 9.50 10.0  10.51  11.03  zinc ions (ppm) 318.33 318.33  318.33  318.33  318.33  318.33  can type S S S S S S ASTM 1053(log10 PV1 = 2.56 PV1 = 2.9 PV1 = 3.73 PV1 = 4.56 PV1 ≥ 4.73 PV1 ≥ 4.73reduction), 30 seconds contact time ASTM 1053 (log10 PV1 = 3.56 PV1 =3.73 PV1 = 4.56 PV1 ≥ 4.73 PV1 ≥ 4.73 PV1 ≥ 4.73 reduction), 5 minutecontact time To each of examples E98 through E103 was added anadditional amount of 10% wt. of AB46 (based on the total weight of theexample composition's constituents, which totaled 100% wt.) as thepropellant constituent, and the reported microbicidal testing wasperformed utilizing the recovered liquid collected immediately after aquantity of the pressurized composition was dispensed from an aerosolcanister

TABLE 1 E104 E105 E106 E107 E108 E109 E110 E111 zinc acetate — — — — — —— — zinc sulfate•7H₂O 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 zincchloride — — — — — — — — ethanol (100%) 35.0  35.0  35.0  35.0  40.0 40.0  40.0  40.0  BTC-65 (50%) — — — — — — — — Onyxide 3300 (33%) — — —— — — — — Neodol 91-6 0.1  0.1  0.1  0.1  0.1  0.1  0.1  0.1 monoethanolamine — — — — 0.07 0.07 0.07 0.07 triethanolamine 0.07 0.070.07 0.07 0.1  0.1  0.1  0.1  sodium citrate 0.2  0.2  0.2  0.2  0.1 0.1  0.1  0.1  Citrasol 502 (50%) — — — — 0.05 0.05 0.05 0.05 NH4OH(29.86%) 0.07 0.07 0.07 0.07 — — — — NaOH (10%) 0.07 0.13 0.16 0.18 0.060.17 0.25 0.32 Triton BX — — — — — — — — Monacor BE — — — — — — — —sodium benzoate — — — — — — — — Silwet Hydrostable — — — — — — — —fragrance — — — — — — — — di H₂O q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.pH 9.99 10.51  11.04  11.5  9.46 9.98 10.5  11.51  zinc ions (ppm)318.33  318.33  318.33  318.33  318.33  318.33  318.33  318.33  ASTME1053 (log10 — — PV1 = 4.44 PV1 = 4.83 — — PV1 = 3.17 PV1 = 4.17reduction) E112 E113 E114 E115 E116 E117 E118 E119 E120 zinc acetate — —— — — — — — — zinc sulfate•7H₂O 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.140.14 zinc chloride — — — — — — — — — ethanol (100%) 42.5  42.5  42.5 42.5  42.5  45.0  45.0  45.0  45.0  BTC-65 (50%) — — — — — — — — —Onyxide 3300 (33%) — — — — — — — — — Neodol 91-6 0.1  0.1  0.1  0.1 0.1  0.1  0.1  0.1  0.1  monoethanolamine — — — — — 0.2  0.2  0.2  0.2 triethanolamine 0.15 0.15 0.15 0.15 0.15 0.27 0.27 0.27 0.27 sodiumcitrate — — — — — — — — — Citrasol 502 (50%) 0.2  0.02 0.02 0.02 0.020.65 0.29 0.14 0.14 NH4OH (29.86%) 0.12 0.12 0.12 0.12 0.12 0.12 0.120.12 0.12 NaOH (10%) 0.06 0.04 0.22 0.37 0.5  — — 0.32 0.47 Triton BX —— — — — — — — — Monacor BE — — — — — — — — — sodium benzoate — — — — — —— — — Silwet Hydrostable — — — — — — — — — fragrance — — — — — — — — —di H₂O q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. pH 8.49 9.5 10.0 10.5  11.5  8.51 9.53 10.46  10.98  zinc ions (ppm) 318.33  318.33 318.33  318.33  318.33  318.33  318.33  318.33  318.33  ASTM E1053(log10 — — PV1 = 5.0 PV1 ≥ 5.17 PV1 ≥ 5.17 — — PV1 ≥ 5.17 PV1 ≥ 5.17reduction) To each of examples E104 through E111 was added an additionalamount of 10% wt. of AB46 (based on the total weight of the examplecomposition's constituents, which totaled 100% wt.) as the propellantconstituent, and the reported microbicidal testing was performedutilizing the recovered liquid collected immediately after a quantity ofthe pressurized composition was dispensed from an aerosol canister Toeach of examples E112 through E120 was added an additional amount of 10%wt. of AB46 (based on the total weight of the example composition'sconstituents, which totaled 100% wt.) as the propellant constituent, andthe reported microbicidal testing was performed utilizing the recoveredliquid collected immediately after a quantity of the pressurizedcomposition was dispensed from an aerosol canister

Certain further pressurized compositions, both comparative compositionsand further example compositions according to the invention wereproduced; these are described on Table 2 and Table 3. These compositionswere formed, and supplied to a sealed dispensing container (can type“S”) and a valve, in the same manner as described with reference to thecompositions of Table 1P, 1P-A, and Table CP.

These compositions were periodically tested at indicated time intervalsfor efficacy against poliovirus Type 1 pursuant to ASTM 1053. Furtherreported on Table 2 was the determination if the tested pressurizedcompositions achieved “complete inactivation”, subsequent to variousintervals of storage and also the concentration of zinc ions in theformulations as measured prior to storage, as well as subsequent toseveral intervals of storage either at room temperature, and at 40° C.

TABLE 2 (Pressurized Compositions) E121 E122 E123 C29 C30 C31 zincsulfate•7H₂O 0.12 0.05 0.05 — — — ethanol (100%) 35.0 37.0 40.0 35.037.0 40.0 Onyxide 3300 (33%) 0.28 0.28 0.28 0.28 0.28 0.28 Neodol 91-60.09 0.09 0.09 0.09 0.09 0.09 monoethanolamine 0.93 0.81 0.79 0.62 0.670.66 triethanolamine 0.09 0.09 0.09 0.09 0.09 0.09 Citrasol 502 (50%)0.11 0.11 0.11 0.11 0.11 0.11 NH4OH (29.86%) 0.09 0.09 0.09 0.09 0.090.09 propellant 7.0 7.0 7.0 7.0 7.0 7.0 di H₂O q.s. q.s. q.s. q.s. q.s.q.s. pH 10.36 10.42 10.42 10.37 10.40 10.42 zinc ions (ppm) 285 182 182— — — can type S S S S S S appearance colorless, colorless, colorless,colorless, colorless, colorless, transparent transparent transparenttransparent transparent transparent ASTM 1053 (log10 reduction)/completeinactivation ? (Yes/No) of PV1 initial - at 0 weeks ≥5.00/Yes ≥5.00/Yes≥5.00/Yes — — — storage (at 40° C.) after 2 weeks ≥5.00/Yes ≥5.00/Yes≥5.00/Yes — — — storage (at 40° C.) after 4 weeks ≥4.27/Yes ≥4.27Yes≥4.27/Yes — — — storage (at 40° C.) after 9 weeks ≥6.00/Yes ≥6.00/Yes≥6.00/Yes — — — storage (at 40° C.) after 10 weeks ≥6.00/Yes ≥6.00/Yes≥6.00/Yes — — — storage (at 40° C.) after 10 weeks — — — =4.58/No=4.91/No =4.66/No storage (at room temperature, 20- 22° C.) zinc ionconcentration (ppm) initial - at 0 weeks 272.8 114.2 114.2 — — — storageafter 4 weeks 259.0 113.0 114.0 — — — storage (at 40° C.) after 10 weeks277.0 111.0 114.0 — — — storage (at 40° C.) after 14 weeks 277.0 — — — —— storage (at room temperature, 20- 22° C.)

As is demonstrated by certain of the compositions of Table 2,pressurized compositions according to the invention exhibited goodstorage stability (the filled pressurized aerosol canisters weremaintained at 40° C. for the duration of the testing) as well asexcellent antimicrobial efficacy against poliovirus type 1 at a 10minute contact time as demonstrated by the reported test results. It isto be noted that the comparative compositions exhibited markedly poorerantimicrobial efficacy following storage at 10 weeks at roomtemperature, as compared to the example compositions according to theinvention. Concurrently as reported above, the concentration ofavailable zinc ions was not observed to change in any significant amountover time, suggesting that the zinc ions did not deposit upon thesurfaces of the aerosol canister over time.

Thereafter the canisters containing the example compositions wereevacuated, and visually inspected for corrosion or rust. No corrosion orrusting was observed either on interior or exterior surfaces of thecanister.

Two of the foregoing example compositions were again tested after havingbeen retained in a pressurized container for in excess of 12 months atroom temperature (20° C.-22° C.), and thereafter tested for microbicidalefficacy. The formulations, the time interval for which they were storedat room temperature, and the test results following the indicated timeinterval (days) are reported on the following Table 3.

TABLE 3 (Pressurized Example Compositions, Long Term Stability Testing)zinc sulfate•7H₂O 0.12 0.05 ethanol (100%) 39.06 40.0 Onyxide 3300 (33%)0.30 0.28 Neodol 91-6 0.093 0.09 monoethanolamine 0.809 0.79triethanolamine 0.093 0.09 Citrasol 502 (50%) 0.11 0.11 NH4OH (29.86%)0.11 0.09 propellant 7.0 7.0 di H₂O q.s. q.s. pH 10.38 10.42 zinc ions(ppm) 272.8 182 can type W S days stored 570 493 ASTM 1053 (log10reduction) 10 minute PV ≥4.27 PV ≥4.27 contact time, ‘dirty’ conditions

As can be seen from the foregoing results the compositions of theinvention exhibited excellent microbicidal efficacy as demonstrated bythe various test results, even wherein reduced amounts of ethanol werepresent as a constituent.

With respect to the reported results of microbicidal efficacy asreported on the foregoing Tables, it is to be understood that each ofthe identified test protocols were performed according to theirpublished standardized protocols, and the results are reported accordingto the identified test protocols. For example in the ASTM E 1052, ASTM1053, EN 131697 tests, the use of the symbol “≥”(greater-than-or-equal-to) indicated that the log₁₀ reduction of thechallenge microorganism was at least equal to the reported result, butmay be greater, while the use of the symbol “=” or the lack of amathematical operator symbol indicated that the log₁₀ reduction of thechallenge microorganism was at least as indicated. In the AOACGermicidal Spray test, the reported results indicate the number ofpositive substrates/total substrates, e.g., a result of “0/60” indicatesthat no positive substrates (survivors) were present within the 60substrate samples tested.

1. (canceled)
 2. (canceled)
 3. (canceled)
 4. (canceled)
 5. (canceled) 6.(canceled)
 7. (canceled)
 8. (canceled)
 9. (canceled)
 10. (canceled) 11.(canceled)
 12. A method of producing an inanimate surface treatmentcomposition which imparts a microbicidal benefit to treated surfaces,the method comprising: supplying room temperature water to a vesselequipped with a stirrer; adding a zinc ion source material to the waterand stirring until dissolved to produce a zinc ion solution; adjustingthe pH of the zinc solution to a pH ranging between about 8 and about 11with a pH adjusting constituent and stirring until homogeneous toproduce a pH solution; adding a lower alkyl aliphatic monohydric alcoholto the pH solution in an amount not in excess of 40% wt of the inanimatesurface treatment composition; adding any auxiliary constituents and, ifnecessary, additional pH adjusting constituent to maintain the pHbetween about 8 and about 11; adding water to bring a final weight ofthe inanimate surface treatment composition to 100% wt and stirringuntil homogeneous to produce the inanimate surface treatmentcomposition.
 13. The method of claim 12, wherein the zinc ion source iszinc acetate.
 14. The method of claim 12, wherein the zinc ion source iszinc sulfate.
 15. The method of claim 12, wherein the lower alkylaliphatic monohydric alcohol is ethanol.
 16. The method of claim 12,wherein the lower alkyl aliphatic monohydric alcohol is present in anamount in excess of 0% wt and up to but excluding 20% wt of theinanimate surface treatment composition.
 17. The method of claim 16,wherein the lower alkyl aliphatic monohydric alcohol is ethanol.
 18. Themethod of claim 12, wherein the pH adjusting constituent is analkanolamine.
 19. The method of claim 18, wherein the alkanolamine isethanolamine.
 20. The method of claim 12, wherein the auxiliaryconstituent comprises a detersive surfactant, other than a quaternaryammonium surfactant compound
 21. The method of claim 20, wherein thedetersive surfactant is a nonionic surfactant.
 22. The method of claim21, wherein the nonionic surfactant is an alcohol ethoxylate.
 23. Themethod of claim 12, wherein a quaternary ammonium surfactant compound isnot present in the inanimate surface treatment composition.
 24. Themethod of claim 12, further comprising adding a quaternary ammoniumsurfactant compound to the zinc ion solution to produce a zinc ion/quatsolution and adding the pH adjusting constituent to the zinc ion/quatsolution.
 25. The method of claim 24, wherein the quaternary ammoniumsurfactant compound is an alkyl dimethyl benzyl ammonium chloride. 26.The method of claim 24, wherein the quaternary ammonium surfactantcompound is an alkyl dimethyl benzyl ammonium saccharinate.
 27. Themethod of claim 12, further adding 80-99.5 parts by weight of theinanimate surface treatment composition and 0.5-20 parts by weight of apropellant to an aerosol container.
 28. The method of claim 24, furtheradding 80-99.5 parts by weight of the inanimate surface treatmentcomposition and 0.5-20 parts by weight of a propellant to an aerosolcontainer.